Heating of dental materials using overtone signatures, absorbing dyes and material properties

ABSTRACT

The invention relates to the application of photon energy to energize dental materials to enhance their physical handling characteristics, efficacy, ability to be delivered, reactivity, polymerization, and/or post-cure mechanical properties, among other attributes.

This application is a continuation of International Application No.PCT/US2018/019260, filed Feb. 22, 2018, the entire contents of which arehereby incorporated herein by reference, which claims priority from U.S.Provisional Application No. 62/462,133, filed Feb. 22, 2017, the entirecontents of which are hereby incorporated herein by reference.

BACKGROUND Technical Field

The invention relates to the application of photon energy to energizedental materials to enhance their physical handling characteristics,efficacy, ability to be delivered, reactivity, polymerization, and/orpost-cure mechanical properties, among other attributes.

Background Information

In many dental procedures, such as root canals or tooth restorations,among others, it is necessary to cleanse and fill a space within a toothin order to effectively restore and seal the space from the exteriorenvironment. During endodontic procedures, practioners usechemomechanical methods to enlarge and cleanse a root canal space.Specifically, practioners use endodontic irrigants to remove debris,remnant pulp tissue and bacteria before filling. Despite advancements inendodontic instruments, endodontic therapy still has an approximate 30%failure rate. These failures have been attributed to bacteriarecolonization/infection of the root canal due to improper cleansing ora failed restoration. Restorative procedures often fail for many of thesame reasons as endodontic procedures, which are poor adhesion of thematerial to the tooth structure, and/or microleakage around therestoration which promote bacteria recolonization/infection. Materialsused during dental procedures, therefore, must be able to adapt to thecomplex geometry of the applied space and bond effectively with thetooth or cavity structure to seal off the area in which the material isplaced. Improving the effectiveness of dental solutions (e.g. endodonticirrigants) and dental materials (e.g. gutta percha, dental compositeresins, i.e. composites, dental sealants, etc) may promote bettercleansing and filling of these voids to increase success rates.

Dental Composite

Dental composite resins offer the dental professional one of the mostcost-effective methods in which to restore a patient's dentition in anaesthetically pleasing manner, which is defined as matching thepatient's natural tooth colors. For cosmetic reasons and to meetconsumer demand, composite resins are a preferred alternative materialto metallic restorations, most specifically amalgams. Composite resinswere first met with doubt and skepticism, which was borne out of amyriad of shortcomings, including the following: poor wear resistance,microleakage, bodily fracture, marginal breakdown, recurrent decay,post-operative sensitivity, inadequate interproximal contacts andcontours, color degradation, and inability to polish or maintain polish.In addition to the physical and mechanical limitations of dentalcomposite resins, placement of dental composites is technique sensitive.The placement of composite requires meticulous attention to theprocedure or it may fail prematurely. Additionally, the tooth must bekept dry during resin placement or the restoration can fail from pooradhesion to the tooth. Composites are placed while still in a soft,dough-like state, but when exposed to light of a certain blue wavelengththey polymerize and harden into the solid filling.

Composite resins generally consist of: acrylate monomers (e.g.triethylene glycol dimethacrylate, TEGDMA, urethane dimethacrylate,UDMA, and bisphenol-A-glycidyldimethacrylate, bis-GMA, etc), inorganicfillers (glasses or ceramics), a photopolymerization system, andpigments and colorants that match tooth colors and shades.Camphorquinone (CQ) is the most common photoinitiator used inphotopolymerizable dental material. CQ has a peak excitation atapproximately 470 nm and is a type II photoinitiator, which requires theaddition of co-initiators to create free radicals to initiatepolymerization. Other photopolymerizable dental materials optionallyinclude type I photoinitiators, such asdiphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) or 1-phenyl1,2-propanedione (PPD), which do not require co-initiators forpolymerization. Irrespective of the photoinitiator and/or co-initiatorused in commercially available products, it is clinically impractical tocompletely convert all free monomers to oligomers and polymers withinthe composite, since the light cannot penetrate more than a couplemillimeters into the composite due to absorption and scatteringproperties of the dental material. If too thick an amount of compositeis placed in the tooth, the deeper composite will remain partially soft,and this soft unpolymerized composite could ultimately lead torestoration failure, leaching of potentially toxic free/unreactedmonomers, and/or leakage of the bonded joint leading to recurrent dentalpathology. To overcome this issue, the dentist is trained to placecomposite in numerous increments, curing each 2-3 mm section fullybefore adding the next increment to maximize polymerization through eachcomposite increment and the complete restoration. In addition, theclinician must carefully construct the composite filling to match thepatient's natural occlusion. If the filling is too high, the patient'sbite may be unnatural, which could lead to chewing sensitivity and/orrestoration failure. Due to the aforementioned issues, improvedcomposite compositions, curing lights, delivery systems, and methods forplacement and enhanced post-cure properties for dental composites isdesirable to aid the clinician and improve the success of therestoration.

A major downside to conventional dental composites (that is documentedin the literature) is the fact that resins demonstrate polymerizationshrinkage. The polymerization of the resin begins the conversion of themonomer molecules into a polymer matrix, which leads to contraction.This bulk contraction (polymerization shrinkage), is seen as avolumetric decrease during the curing/polymerization process. Thematerial transforms in phases; from a viscous, to viscous-elastic, toelastic in nature. In the viscous stage, stress is non-existent. Duringthe viscous-elastic stage, however, stresses occur in the material andat the material-tooth interface. Shrinkage stresses are transferred tothe cavity walls of the tooth due to volumetric changes in thecomposite. These stresses, and the resulting polymerization shrinkage,can be influenced by material selection, filler content, irradiance andduration of the applied polymerization light source, curingcharacteristics of the resin, water sorption, and cavity prepconfiguration. Many options have been proposed to limit internal toothstresses, including the following: the use of liners and bases,alteration of polymerization light, irradiance waveform, incrementallayering, increased filler content, and modification of bondingtechniques. Unfortunately, none of these can fully compensate for theeffects of this phenomenon.

The effect of lowering viscosity to improve adaptation of the compositeand to improve ease of placement has been shown to be important. This isthe primary basis for the development of flowable resin composites andflowable liners. These flowable composites achieve their lower viscosityprimarily by a reduction in reinforcing filler content and changes inthe matrix chemistry. A variety of studies have shown that lowerviscosity composites can improve adaptation and reduce microleakage. Theuse of flowable composites has also been touted as a way to ensure amore intimate contact with both the dentin bonding agent and internalsurfaces of the prep, and to augment the seal obtained by a composite atthe cavosurface margin. With some types of restorations, it can bedifficult to achieve complete interfacial sealing between the toothstructures and composites.

One potential way to improve sealing would be to use lower viscosityflowable composites; however, these flowable composites are notgenerally considered as durable as higher viscosity materials, due tothe lower levels of reinforcing filler particles present. A secondapproach is to use a flowable liner in conjunction with regularcomposites. A third alternative is to use conventional/highly filledcomposites that have been heated to lower their viscosity. In this lastapproach, higher durability conventional composites could be used, whileutilizing their reduced viscosity to form more intact interfaces withtooth tissues and eliminates the need for a flowable liner. Also, thisthird alternative is seen as advantageous since flowable resins are lessfilled than traditional composites, and therefore exhibit highershrinkage rates due to the decreased filler content. This could beproblematic in restorative techniques when a large volume of flowablecomposite is used in an attempt to improve the seal and marginaladaptation of the composite.

As stated earlier, many polymer resins exhibit lower viscosity when theyare heated. The theoretical basis for this behavior is that thermalvibrations force the composite monomers or oligomers further apart,allowing them to slide by each other more readily. Studies have shownthat heating general polymers and resin composites lowers viscosity andthereby improves adaptation. Deb et al. (Dent Mater. 2011 April;27(4):e51-9) have shown that increasing dental composite temperaturelowers viscosity as indicated by decreased film thickness. Similarresults were found by Broome (Dent Adv. 2006 January; 4). As such,preheating composites has been the focus of research in recent years, aspreheating improves the physical and mechanical properties of the resin.Preheating of dental composites has been shown to reduce the viscosityand potentially increase the post-cure microhardness of the compositeresin. Currently available devices used to aid the clinician inpre-heating composite rely primarily on conductive heat transfer andhave many downsides, including long heat up times, not heating at thepoint of delivery which causes the composite to cool and potentiallyreach room temperatures depending on procedural application times, thelack of being able to heat multiple composites quickly, and the lack ofbeing able to heat the composite once placed within the restoration;among other challenges and limitations.

Effect of Elevated Temperatures on Composite Properties after Curing

There is concern about the effect preheating has on the properties ofphotopolymerizable dental materials. A few studies have investigated theconversion of double bonds (a measure of how completely thepolymerization reaction progresses) and hardness of the composite afterthe preheating treatment. These studies are important in determining howquickly and completely the composite polymerizes. Preheating appears toeither improve conversion and hardness or it produces no negativechanges. Increased conversion generally equates to better mechanicalproperties of the polymeric materials and composites. Therefore,preheating may lead to more durable composite restorations. Furthermore,there has been concern that the higher temperature of preheatedcomposite would lead to greater shrinkage of the composite during andafter curing. Elhejazi (J Contemp Dent Pract. 2006 Jul. 1; 7(3):12-21)showed that raising the temperatures of resin composite led to greatershrinkage. In response to this concern, it was suggested that thepreheated composite be allowed to cool for a period of about 15 secondsafter placement but before curing. Another concern expressed in theliterature was that subjecting the composite to preheating cycles wouldreduce the shelf life of the unused composite. However, Daronch et al.(J Esthet Restor Dent. 2006; 18(6):340-51) showed that neitherpreheating cycles nor extended preheating for 24 hours caused anysignificant changes in monomer conversion. Although some studies existthat demonstrate preheating does not negatively impact dental materials,research is conflicting and not comprehensive for all dental materials.

Obturation

Successful root canal therapy is dependent on many factors. It begins byremoval of all the organic substrate from the canal. This includesremoval of the coronal pulp tissue and radicular pulp tissue. Thecoronal pulp tissue is removed by performing complete access andidentifying straight-line access to the radicular pulp tissue. This, inturn, allows the practitioner to remove the radicular pulp tissue withendodontic files and irrigation. Irrigation is arguably the mostimportant part of endodontic therapy as chemomechanical instrumentationalone leaves approximately 30% of the root canal untouched. Therefore,the importance of effective irrigation in root canal preparation cannotbe overemphasized, and enhancing the activity/efficacy of endodonticirrigants is desired.

Finally, the last objective is preventing reinfection by obtaining athree-dimensional obturation of the canal. For increased endodontictreatment success, the canal system must be effectively sealed coronallyand apically. The apical seal is the principal barrier to leakage. Thereare many different obturation techniques; no one technique has beenidentified as clearly superior. It has been shown that adding heat toobturation increases success rates and allows for obturation of canalirregularities and anatomy that traditional techniques may not seal.Characteristics of successful obturation are defined and categorized asthe three-dimensional filling of the entire root canal system as closeto the cemento-dentinal junction as possible; i.e., without grossoverextension or underfilling in the presence of a patent canal. Minimalamounts of root canal sealers are used in conjunction with the corefilling material to establish an adequate seal.

Controversy has surrounded root canal obturation for many years.Clinicians and academics alike have researched, studied, applied, andcompared many warm obturation techniques, and no single technique hasbeen proven superior to another, leaving clinicians to experiment andform preferences through trial.

Following endodontic obturation, a coronal restoration is completed torestore the tooth shape and occlusal surface. There is reasonableevidence to suggest that coronal leakage through improperly placedrestorations is a significant contributing factor in endodontic therapyfailure. Thus, there remains an unmet need for new methods,compositions, and device that improves upon dental material applicationand the curing of dental materials and for performing the aforementioneddental procedures.

BRIEF SUMMARY

A benefit of the embodiments of the invention described herein is thatvia the application of photon energy to the dental composite or dentalcomposite's container, the material is rapidly and efficiently heatedchairside above ambient temperature. This inventive concept also appliesto all dental materials. In comparison to commercially availablecomposite warmers, the disclosed invention is highly efficient,especially when there is high conversion efficiency from photon energyto heat. Elevating the dental material's temperature, for example dentalcomposite resins, improves the material's physical handlingcharacteristics and ability to be delivered, obviating the need offlowable composites as the dental composite is capable of exhibitingviscosities similar to flowable composites but does not suffer from thenegatives of flowable composites (high shrinkage, low wear retention,low hardness, etc.). Furthermore, since the invention allows for theapplication of photon energy to the dental materials once it is placed,improved handling characteristics can be achieved even after dispensingthe material from the tool or wand. Additionally, improved flowabilityand adaptation can allow for a filling smaller voids in the tooth andperforming minimally invasive restorations. Furthermore, heatingcomposite would allow manufacturers to develop and commercialize morehighly filled composite, which heretofore has not been possible due toextrusion and manipulation constraints of highly filled materials.Normally, increasing the filler content would make the composite toothick and hard to work with, however by heating using photon energy, theflowability will return to that of less filled or even flowablecomposites while still maintaining the benefits of a highly filledcomposite (i.e. reduced shrinkage stress, increased durability). Thus,the disclosed invention further improves coronal restorations andthereby improves clinical outcomes.

As described herein, a dental material is provided that can be heated toincrease the flowability of the material to ease the application andconformance of the material to the tooth surface to which the materialis applied. Further, as a result of the heating of the material, whencured the composite has increases in hardness and durability, withoutany deterioration in the cured dental materials compared to dentalmaterials placed without the use of the methods described herein.

In addition, the disclosed invention utilizes photon energy to quicklyheat endodontic irrigants above ambient temperature and to promotephotochemical effects thereby making the irrigants more efficaciousduring use. Furthermore, a major benefit of the disclosed invention isthat the use of photon energy does not have any deleterious impact ondental materials or dental composite resins specifically. Moreover, theinvention described herein allows for gutta percha, or a similarobturation material, to be delivered and applied within the root canalspace with improved handling and lower viscosities than previouslyachieved. By lowering the viscosity and improving the delivery, theinvention allows the clinician to more reliably gain a three dimensionfill of the complex root canal anatomy and significantly reduceendodontic treatment failures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of near infrared absorption bands of common organicbonds and functional groups. The figure details the peak absorbancebands and respective first, second and third overtone absorbance bandsof the organic and functional group structures.

FIG. 2 is an area-intersect figure. A1=area-under-the-curve (AUC) forthe normalized additive spectra, A2=AUC for the normalized photon energysource spectra, A3=area-intersection of the additive's spectra and thephoton energy source's emission spectra. In some aspects, A3 is at least10% of either A1 or A2. In some aspects, A3 is at least 25% of either A1or A2. In some aspects, A3 is at least 50% of either A1 or A2.

FIG. 3 is a graph of the absorption of three commercially availabledental composite resin materials (also synonymously called dentalcomposite materials) and a comparison to poly(methyl methacrylate) (i.e.acrylic). This figure demonstrates the similarities of dental compositenear infrared absorbance characteristics and acrylic, due to thepresence of acrylate-based monomers within the composite resin'scomposition. These absorbance characteristics can be exploited forefficient heating using photon energy. For example, targeting higherabsorbance bands with photon energy will result in quicker heating ofthe dental material.

FIG. 4 is graph of the absorbance of gutta-percha and a highly filleddental composite material. These absorbance characteristics can beexploited for heating using photon energy, where higher absorbance wouldtranslate to increased photon energy conversion efficiency and fasterheating rates.

FIG. 5 is a graph of absorption curves for polycarbonate plastic withdifferent pigments added to the thermoplastic resin. This figuredemonstrates the dependency of near infrared absorbance depending on thecolor of a material, not solely on the material itself. Thus,thermoplastic colorant/pigment additives can be used to alter theabsorbance characteristics of the material container. These absorbancecharacteristics can be exploited for heating using photon energy, wherehigher absorbance would translate to increased photon energy conversionefficiency and faster heating rates.

FIG. 6 is a graph of the internal temperature within a composite compuleusing a commercially available composite warmer. This figuredemonstrates how current composite warmers require long warm up times toreach ideal temperatures compared to the invention.

FIG. 7 is a graph of the time to heat three different commerciallyavailable dental composites using various photon energy sources andspatial arrangements. This figure demonstrates that optical output powerdoes not necessarily translate solely to heat rates, as thermaldiffusion also plays a critical role in the heat distribution andtransfer within the composite and composite compule itself. Thus,practicing the invention requires utilizing proper optical power andspatial orientation of photon energy sources directed toward the dentalmaterial and/or dental material container for optimal performance and toconserve input power (i.e. efficiency).

FIG. 8 is a graph of viscosity vs. shear rate for various composites atdifferent temperatures. This figure demonstrates that at all shear ratesthe viscosity of commercially available dental composites is reducedwith increasing temperature, and the reduced viscosity improves thehandling characteristics and delivery to the tooth and/or cavity.

FIG. 9 is a graph of flowability of highly filled composite versustemperature compared to a flowable composite at room temperature. Thisfigure demonstrates that heating of highly filled composites canincrease the flowability of highly filled composites to be equivalent orgreater to flowable composites, thereby demonstrating that a cliniciancan use heat to obviate the need of using a flowable composite as aliner in the tooth cavity restoration.

FIG. 10 is a graph of post-cure microhardness when various commerciallyavailable dental composites are maintained and cured at varioustemperatures. This figure demonstrates that elevated temperatures aboveambient increases the polymerization of dental composites during curingresulting in higher microhardness on the top and bottom of a 2 mm puck.

FIG. 11 is a graph of post-cure monomer and oligomer conversion whenvarious commercially available dental composites are maintained andcured at various temperatures. This figure demonstrates that elevatedtemperatures above ambient increases the degree-of-conversion ofmonomers to oligomers and polymers within dental composites duringcuring, which results in higher microhardness on the top and bottom of a2 mm puck.

FIG. 12 is a graph of microhardness values post-cure of highly filledcomposites subjected to various multispectral patterns of applied photonenergy (850 nm) and curing light (405 nm and 470 nm simultaneously). Astatistically significant difference (p<0.05) was observed between G3top vs G1 top, and G4 top vs G1 top. This figure demonstrates that theaddition of photon energy within the disclosed wavelength range enhancesthe polymerization and degree-of-conversion translating to increasedmicrohardness values post-cure.

FIG. 13 is a graph of post-cure microhardness values of variouscommercially available dental composites after the application ofextended elevated temperatures from either photon energy or an ovencompared to room temperature. Data demonstrates that 1 hour applicationsof elevated temperatures (80° C.) resulting from photon energy, or anoven, did not negatively impact the composite as microhardness valueswere not statistically significantly different compared to roomtemperature (untreated) composite post-cure.

FIG. 14 is an isometric view of a delivery device according to oneexemplary embodiment of the invention.

FIG. 15 is a partially broken away bottom plan view of a dispensing tipand compule of the device of FIG. 14 showing retention of the compuleand spatial orientation of the photon energy sources directed towardsthe dental container containing a photopolymerizable dental material.

FIG. 16 is an isometric view of a delivery device according to anotherexemplary embodiment of the invention.

FIG. 17 is an exemplary embodiment of a package consisting of at leastthree photon energy emitters (i.e. LEDs) for use in a multispectraldevice, which emits at least two discrete emission spectra to curedental composite materials and for the application of photon energy forheating. The left image is a top view of the package showing theorientation of three photon energy emitters (i.e. LEDs) on a clovershape PCB. The right image is a cross-section of the package showing thecentrally located photon energy emitter 32 c (i.e. LED) located on aplane parallel to the clover PCB; here two of the three LEDs located onthe clover PCB are shown.

FIG. 18 is an exemplary embodiment of a package of photon emitters foruse in a multispectral device that emits at least two discrete emissionspectra for curing dental composite materials and for the application ofphoton energy for heating.

FIG. 19 is an exemplary embodiment of a package of photon emitters foruse in a multispectral device, which emits at least two discreteemission spectra for curing dental composite materials and for theapplication of photon energy for heating.

FIG. 20 is a graph showing the NIR reflection values compared to theinternal temperature of a dental material exposed to 15 s of photonenergy within the specified photon energy band from a Vishay VCNL4010sensor (Fully Integrated Proximity and Ambient Light Sensor withInfrared Emitter, I²C Interface, and Interrupt Function) obtained fromvarious colored commercially available dental containers. This figuredemonstrates that at a fixed distance from the sensor, there is a strongcorrelation (R²=0.97) between the measured NIR reflectance and theobject's change in temperature after 15 seconds of exposure to an NIRLED (wavelength, power, time, and distance were all held constantbetween objects). The sensor, therefore, can be used to determine theamount of photon energy needed to heat a given dental material, or amaterial's container, to a desired temperature and optionally maintainthe desired temperature over a period of time. Additionally, thesensor's measured value can be a “fingerprint” to identify the insertedobject to implement a closed platform system (i.e. the device would onlywork with a specific material or material container).

FIG. 21 is a graph showing the post-cure microhardness values of filteksupreme composite when subjected to multispectral light bysimultaneously applying photon energy within the disclosed wavelengthband and 470 nm light for curing. The asterisk designates statisticallysignificantly different values compared to the “470 nm” group. Thisfigure demonstrates that the addition of photon energy within thedisclosed wavelength range enhances the polymerization anddegree-of-conversion translating to increased microhardness valuespost-cure.

FIG. 22 is a graph showing the absorption coefficient for biologicaltissues at various wavelengths, of particular importance to teeth areoxyhemoglobin, protein, water, and hydroxyapatite. Althoughhydroxyapatite and water exhibit low absorption coefficients forcommercially available curing light spectra, i.e. peak emission at 470nm, oxyhemoglobin absorption coefficient is 1000-10000 times higherabsorbance than the disclosed photon energy spectra, and is whycommercially available curing lights pose concern for intrapulpaltemperature rises and safety. The disclosed invention, therefore, canutilize photon energy between 520 nm and 2500 nm to increase compositemicrohardness (FIG. 21), decrease oxyhemoglobin and pulp absorbance, andimprove clinical efficacy and safety.

FIG. 23 is a graph showing the increase in dental composite (Grandio SO,VOCO) temperature when a photon energy absorber/dye was added at varyingconcentrations. Statistically significantly improved heating wasobserved with concentrations ≥0.1% of the LUNIR1 dye. The figuredemonstrates that adding a photon energy absorbing dye to the compositesignificantly improves the energy conversion efficiency of photon energyto heat as evident by a substantially increased temperature observedafter exposure to about 15 seconds of photon energy.

FIG. 24 is a graph showing the increase in dental composite (FiltekSupreme) absorbance when a photon energy absorber/dye (ICG) was added atvarying concentrations. Statistically significantly greater absorbancewas observed with concentrations >1 ppm of the ICG dye. The figuredemonstrates that adding a photon energy absorbing dye to the compositesignificantly increases the absorption characteristics of the dentalmaterial. This increased absorbance can be targeted using photon energyto increase heating rates of materials.

FIG. 25 is a graph showing the heating profiles obtained frompolymethylmathacrylate (PMMA) resin, with or without differing absorbingdyes incorporated therein, subjected to a constant photon energy sourceat 940 nm for about 30 seconds. Temperature measurements were recordedfor about 60 seconds total. The graph demonstrates that by incorporatingdyes that have higher absorbance values commensurate with the appliedphoton energy source, the heating rates and overall gain in temperaturecan be substantially increased compared to resin with no dye or lessabsorbing dyes/pigments. Additionally, once photon energy is stopped,the material temperature decreases readily, as evident by the quicklydecreasing temperature measurements for the NIR dye in PMMA between 30seconds and 60 seconds. This is an additional advantage of the inventionas materials can cool quicker when photon energy is stopped. Thus, if ahot material is warmed in a disclosed inventive device, the device canbe turned off and the material will cool quickly before touching.Conversely, commercially available warming units maintain their heat forsignificantly longer periods of time, as they typically heat metalblocks which then primarily transfer heat to the material viaconduction.

FIG. 26 is a graph showing the post-cure microhardness values of acommercially available composite (Ivoclar Evo-Ceram A2 shade) with orwithout an additional photoinitiator (660HNu) and co-initiator (BorateV)at various concentrations when subjected to curing emissions ofequivalent total optical power. An improvement in microhardness valueswas seen for Ivoclar Evo-Ceram additionally incorporating 0.005% 660HNuand 0.05% BorateV subjected to simultaneous 470 nm and 660 nm. Thisfigure demonstrates that improving polymerization and microhardnessvalues is dependent on the concentration of the additionallyincorporated photoinitiator and coinitiator. Additionally, a visiblecolor change from green/blue to standard A2 shade was visualized afterphotopolymerization for the various compositions, as shown in FIG. 27.In particular, the green/blue color was unnoticeable post-cure for660HNu concentrations equal to or below 0.05%. Thus, theseconcentrations can be used to provide a visible indication of acomplete/successful cure to the clinician. Conversely, remnantgreen/blue color is observed in the 0.1%660HNu samples post-cure andthus would not be suggested for aesthetic dental use.

FIG. 27 demonstrates that any introduced color by incorporated additivescan be lost upon curing to indicate a successful/complete cure to theclinician.

FIG. 28 is an isometric view of a delivery device according to anotherexemplary embodiment of the invention.

FIG. 29 is an isometric view of a delivery device according to anotherexemplary embodiment of the invention. The inset image shows thecompule/material container located with the device's receptacle forreceiving the compule/material container.

FIG. 30 is a cross-sectional view of part of the device. The insetimages shows the compule/material container located with the device'sreceptacle for receiving the compule/material container, as well as howthe device's plunger makes contact with the dental material container toextrude the dental material therein.

FIG. 31 is a cross-sectional view of the isometric side-profile imagewithin FIG. 25.

FIG. 32 is an exploded view of the device shown in FIG. 24 showing thevarious components of the device.

FIG. 33 is an isometric cross-sectional view of a multispectral curinglight device according to one exemplary embodiment of the invention.

FIG. 34 is a bottom view of a multispectral curing light deviceaccording to one exemplary embodiment of the invention.

FIG. 35 is an exemplary embodiment of a package consisting of at leastthree photon emitters (i.e. LEDs) for use in a multispectral devicewhich emits at least two discrete emission spectra for curing dentalcomposite materials and for the application of photon energy forheating.

FIG. 36 is a graph showing the absorbance versus wavelengthcharacteristics of one exemplary embodiment of the invention for adental material container, wherein a thermoplastic resin (polycarbonate)incorporates a photon energy absorption dye (Epolite 7657) that has highabsorbance from about 800 nm to about 1100 nm and below 550 nm (sampleis 2 mm thick). This dye/additive simultaneously results in highabsorbance within the photon energy range, and thus can be targeted forincreased container and/or material heating rate using photon energyemitters, as well as within the blue light range (400-500 nm), tosuccessfully block polymerization light from photopolymerizing thedental material within the container.

FIG. 37 is a block diagram showing the generalized functioningcomponents of one exemplary device used to heat, control and identifythe dental material and/or dental material container. The dentalmaterial and/or dental material container's temperature can becontrolled and maintained via the use of a sensor feedback loop.Additionally, the sensor may be used to ensure that photon energysources only emit photon energy if a material or container is present.Lastly, the sensor may be used to specifically identify variousmaterials and/or containers based on the feedback.

DETAILED DESCRIPTION

The following paragraphs define in more detail the embodiments of theinvention described herein. The following embodiments are not meant tolimit the invention or narrow the scope thereof, as it will be readilyapparent to one of ordinary skill in the art that suitable modificationsand adaptations may be made without departing from the scope of theinvention, embodiments, or specific aspects described herein. Allpatents and publications cited herein are incorporated by referenceherein in their entirety.

For purposes of interpreting this specification, the following terms anddefinitions will apply and whenever appropriate, terms used in thesingular will also include the plural and vice versa. In the event thatany definition set forth below conflicts with any document incorporatedherein by reference, the definition set forth below shall control.

The term “room temperature” or ambient temperature as used herein refersto common ambient temperatures ranging from about 20° C. to about 27° C.

The term “treating” refers to administering a therapy in an amount,manner, or mode effective to improve a condition, symptom, or parameterassociated with a disorder. In some aspects, treating refers to thetreatment of a dental ailment such as a cavity.

The term “prophylaxis” refers to preventing or reducing the progressionof a disorder, either to a statistically significant degree or to adegree detectable to one skilled in the art.

The term “substantially” as used herein means to a great or significantextent, but not completely.

As used herein, “a” or “an” means one or more unless otherwisespecified.

Terms such as “include,” “including,” “contain,” “containing,” “has,” or“having,” and the like, mean “comprising.”

The term “patient” or “subject” refers to mammals and humans. Thus, inone aspect, the subject is a mammal, or a mammal in need thereof. In oneaspect, the subject is a human, or human in need thereof. In one aspect,the human or human in need thereof is a medical patient. The subject canbe from ˜0 years of age to 99 years of age or older.

Described herein are methods for applying photon energy to heat dentalmaterials and dental material housings or containers. Also describedherein are dental material compositions and dental material containersor housings having enhanced heating properties and photopolymerizationproperties based upon the inclusion of heating additives andphotopolymerization enhancer systems. Further described herein aredevices capable of applying specific wavelengths of photon energy forheating, delivering, and curing a dental composition (e.g., the dentalcompositions disclosed herein). Also described herein are methods fortreating patients with the methods and devices disclosed herein.Although one example or embodiment may discuss, or specifically relateto, a certain application or aspect of the invention, it is understoodthat the example or embodiment may additionally relate to and envisionother detailed aspects of the invention. For example, certain devices ormethods may be discussed with relation to dental composite materials,however, the same devices or methods may be applicable to other dentalmaterials in general.

The inventors report that photon energy between 0.49 eV-2.38 eV (i.e.2500 nm-520 nm), between 0.49 eV-1.90 eV (i.e. 2500 nm-650 nm) orbetween 1.23 eV-2.06 eV (i.e. 1000 nm-600 nm) can be used to enhancedental materials' handling properties, mechanical properties, andperformance properties with high conversion efficiency. Dental materialsinclude but are not limited to: composites, resins, glass ionomerresins, cements, cavity liners, endodontic irrigants, endodonticobturation materials, gutta percha, anesthetic, and sealants.Accordingly, the invention described herein includes a method forheating dental materials, a method for improving the polymerization ofphotopolymerizable dental materials, dental material heating anddelivery devices, dental material heating and curing devices, and dentalmaterial compositions.

Photon energy outside the specified range of 0.49 eV-2.38 eV (i.e. 2500nm-520 nm) is still envisioned by the invention to enhance dentalmaterials' handling properties, mechanical properties, and performanceproperties with high conversion efficiency. In particular, the use ofultraviolet light may be utilized as ultraviolet wavelengths have highphoton energy (specifically ultraviolet A wavelengths: 315 nm-400 nm,3.93 eV-3.09 eV), and many materials exhibit inherently high absorbancebelow 400 nm. Although these other wavelengths are possible, someparticular embodiments described further herein utilize photon energywithin the specified range of 0.49 eV-2.38 eV (i.e. 2500 nm-520 nm) aswavelengths below 400 nm can have a deleterious impact on the dentalmaterial, specifically photopolymerizable dental materials, and are apotential safety concern due to ionization. A specific concern is thephotopolymerizing of dental materials, which may occur if ultravioletlight is utilized directly on the material itself, however, in someembodiments, ultraviolet light can be utilized to heat the dentalmaterial's container, providing that the dental material's container hasan optical density value of at least two for wavelengths below 400 nm,i.e. the dental material's container transmits <1% of light below 400nm. Conversely, in some other embodiments, ultraviolet light may be usedon other non-photopolymerizable dental materials, specificallyendodontic irrigants, to enhance their performance properties viaphotochemical effects.

Method for Applying Photon Energy to Heat Dental Materials

Some embodiments described herein are methods for heating dentalmaterials above ambient temperature using a photon energy withoutdeleteriously affecting the dental material. One embodiment is a methodof heating a dental material with photon energy between 0.49 eV-2.38 eV(i.e. 2500 nm-520 nm) to quickly heat the dental material to an elevatedtemperature above ambient temperature. In some aspects, the dentalmaterial is heated to a temperature of about 50° C. to about 250° C. Insome aspects, dental material is heated to a temperature between about50° C. and about 100° C. In some other aspects, the dental material isheated to a temperature between 60° C. and about 80° C. In some aspects,the applied photon energy is between 1.23 eV-2.06 eV (1000 nm-600 nm).In some embodiments, the photon energy to heat the dental material isapplied prior to application of the dental material. Other photon energywavelengths may be utilized by tuning the applied photon energy to thefundamental absorption frequency/wavelength and/or an overtonevibrational band of the dental material or the dental material'scontainer. In particular, any resonant frequency above the fundamentalfrequency is referred to as an overtone. In the electromagneticspectrum, overtone bands are multiples of the fundamental absorptionfrequency. Because energy is proportional to the frequency absorbed,which in turn is proportional to the wavenumber, the first overtone thatappears in the spectrum will be approximately twice the wavenumber ofthe fundamental. That is, the first overtone v=1→2 is approximatelytwice the energy of the fundamental, v=0→1. For example, a vibratingdiatomic molecule such as hydrochloric acid (HCl), with a fundamentalabsorption at 3465 nm, will have its first overtone absorption band at1733 nm (actually observed at 1764 nm), second overtone absorption bandat 1155 nm (actually observed at 1198 nm), third overtone absorptionband at 866 nm (actually observed at 915 nm), and fourth overtoneabsorption band at 693 nm (actually observed at 746 nm). Thus, to obtainequivalent vibrational motion, significantly more energy will berequired at the first overtone compared to the energy needed at thefundamental absorption frequency/wavelength. As increased molecularvibrations results in heat generation, it is possible to target thefundamental absorptions and/or overtone bands to heat objects andmaterials.

With regard to dental materials, the fundamental absorption bands aretypically outside the specified photon energy range (0.49 eV-2.38 eV,i.e. 2500 nm-520 nm). Therefore, overtone bands of the dental materialsare targeted by some embodiments described herein. Specifically forphotopolymerizable dental materials (i.e. composites, resins, cements,sealants, etc), the application of photon energy prior to use or duringuse (i.e. in vivo) quickly heats the material above ambient temperaturebut does not prematurely cure or negatively impact thephotopolymerizable material pre or post cure, which can occur if theapplied photon energy activated the material's incorporatedphotoinitiator.

Clinically, heated photopolymerizable materials are advantageous as theyexhibit increased flowability to ease the application and conformance ofthe photopolymerizable material to the tooth surface. This same conceptholds true for all dental materials in general. Additionally, thephotopolymerizable material's mechanical properties may be enhanced byapplying photon energy during curing, or just before curing, to increasethe temperature, which has been shown to increase post-cure properties(degree-of-conversion and microhardness), compared to standard curing.Thus, in some aspects described herein the applied photon energy is at aseparate wavelength from the absorption peak used to active thephotopolymerizable material's photoinitiator.

The type and amount of photon energy to be applied to the dentalmaterial for a desired heating can be determined based upon theabsorbance overtone regions for various components (e.g., molecules andbonds). For example, various components and their respective overtoneregions is illustrated in FIG. 1. Most components have absorbance inmore than one overtone region, and thus some embodiments relate to theapplication of photon energy to these composites utilizing wavelengthsin the combination band region, primary absorption band, or any of theovertone regions contained within 0.49 eV-2.38 eV (i.e., 2500 nm-520nm). In some embodiments, the utilized photon energy is between 1.23eV-2.06 eV (i.e., 1000 nm-650 nm).

In some embodiments, the applied photon energy is in the third overtoneregion, or greater overtone, or other component absorptioncharacteristics within the specified photon energy ranges/wavelengths,to provide certain advantages with regard to the degree and speed ofheating that can be accomplished without overly high energyrequirements. The disclosed embodiments are highly efficient atconverting energy from a power source to heat using photon energy thatis tuned to the dental material and/or dental materials container.

Photon emission within the third overtone band can be accomplished withcurrently existing LED technology whereas emission of photons in the1^(st) or 2^(nd) overtone band would require diode lasers and muchhigher expense with much lower optical energy output. Fundamentally,shorter wavelengths of light have greater frequencies and higher photonenergy. Given the relationship between wavelength and frequency—thehigher the frequency, the shorter the wavelength—it follows that shortwavelengths are more energetic than long wavelengths. As such, the thirdovertone, despite having a lower absorbance in certain instances,utilizes wavelengths that have high energy and are can demonstrate moreeffective and efficient heating properties. In addition, withinformation regarding the components utilized in a composite material,the particular wavelengths in the selected region can be specificallytargeted onto the composite to efficiently affect the heating of thecomposite material in the wavelengths where the molecules and bonds havethe highest absorption.

In some embodiments, photon energy is applied to dental materialsincluding but not limited to: anesthetic (reducing pain duringinjection), gutta-percha (for endodontic root canal obturation), dentalcomposites, sealants, cements, cavity liners, and glass ionomer resins(e.g., lowering viscosity, improving handling characteristics,decreasing voids, and improving mechanical properties post-cure) andendodontic irrigants (increasing efficacy and reactivity).

Thus, some embodiments the photon energy herein is applied utilizingdevices that are specifically configured for the efficient heating of adental material sample.

Method for Applying Photon Energy to Enhance the Material's Performanceor Reactivity

One embodiment is a method of applying photon energy to a dentalmaterial to enhance the material's performance or reactivity viaphotochemical effects. This method is succinctly different and separatefrom photodynamic therapy and the use of photosensitizers. One aspect isthe use of photon energy within the specified range tophotopolymerizable dental materials, which further increases themechanical properties of the dental materials. Without being bound byany theory, this can be performed using the two-photon effect if theproper wavelengths or electron volts are matched to the photoinitiator.For example, to polymerize a material containing camphoroquinone via thetwo-photon effect, applying photon energy in a band from 880 nm-960 nmcan be utilized.

Another embodiment is the use of photon energy to stimulatephotochemical effects including photodegradation (i.e. the alteration ofmaterial by light, which can include oxidation and free radicalgeneration), photobleaching (i.e. photochemical alteration of a dye toreduce or remove the dyes visible color or fluorescent properties) orphotocatalysis (i.e. the acceleration of a chemical reaction by light)of a dental material. Clinically, this may be useful to promotedisinfection properties, esthetic properties, and safety. With regard toendodontic irrigants, the application of photon energy can be used toenhance the disinfection properties of commonly used irrigations such assodium hypochlorite or chlorhexidine whereby the reactivity or freeradical generation is increased by photon energy at certain wavelengths.The aforementioned methods above can be further enhanced by theincorporation of additives to the dental material further describedherein.

Additives for Improved Heating Via Enhanced Energy Conversion Efficiencyand Heat Transfer

Another embodiment includes a method for improving the heating of adental material by adding one or more heating additives to the dentalmaterial or dental material container. In some aspects, the heatingadditive is a photon energy absorption enhancer or a thermalconductivity enhancer. As described herein, the addition of heatingadditives including certain photon energy absorption enhancers (e.g.,absorbing dyes) and thermal conductivity enhancers to the dentalmaterial and/or the dental material's container to increase the photonenergy absorption, energy conversion efficiency from photon energy toheat, and/or material heating rate. In some aspects, the methodsdescribed herein include adding one or more heating photon energyabsorption enhancers, one or more thermal conductivity enhancers or anycombination thereof to a dental material or dental material container.

Suitable photon energy absorption enhancers exhibit one or more of thefollowing properties: high absorbance between, (e.g., 0.49 eV-2.38 eV(i.e., 2500 nm-520 nm)), high ultraviolet A absorbance between 3.93eV-3.09 eV (315 nm-400 nm), biocompatible, doesn't impart an unnaturaltooth color to the material, compatible with the material and/or thecontainer, stable, demonstrates heat stability (e.g., if used forinjection molding), soluble and dispersible within the material and/orcontainer, doesn't negatively affect the material's performance, and hasa high conversion efficiency from photon energy to heat, or combinationsof properties thereof. Additives that absorb ultraviolet light can beadvantageous to use as many ultraviolet absorbing dyes are colorless,however, other dyes that absorb between 0.49 eV-2.38 eV may also becolorless or impart acceptable color to the dental material. Forexample, additives that impart a slight yellow or tan color may beacceptable to include in various shades of dental materials that areslightly yellow or tan. Exemplary and non-limiting photon energyabsorption enhancers that satisfy some of the above properties includethe following dye classifications: cyanine, polycyanine, fluorones,amminium, trisaminium, metal dithiolene complexes, anthroquinone,peri-arylenes (i.e., sexterrylenes and sexterrylenetetracarboxylicbisimides), squaraines, phthalocyanines, phthalocyanines metalcomplexes, polymethine cyanines, porophyrines, chlorines,benzochlorines, thiazines, quantum dots, and single walled carbonnanotubes. Suitable commercially available dyes meeting one or more ofthe aforementioned criteria include, but are not limited to: Cy3, Cy5,fluorescein, indocyanine green, methylene blue, toluidene blue,absorbing dyes from Luminochem (e.g., LUNIR8/1; Budapest, Hungary),absorbing dyes from Epolin (i.e., Epolite 4113, 4831, 4019, 7809, 4105,3130, 3169, 3036, 4019, 4129, 4113, 5262, 5839, 6661, 6158, 5636, 6084;Newark, N.J.) absorbing dyes from QCR Solutions (preferably NIR806F,NIR856A, NIR886A, NIR848A, NIR949A, NIR728A, NIR700A, NIR739B; Port St.Lucie, Fla.). Below is a structure of Cy3 and Cy5, with higherwavelength cyanine dyes sharing a similar structure, and areadvantageous since cyanine dyes have been shown to be biocompatible.

-   -   Absorbing cyanine dyes (Cy3 and Cy5)

In another aspect, the photon energy absorption enhancer is added to thedental material or dental material's container at a concentration toyield an absorbance/optical density value greater than or equal to 1 andat a photon energy within the disclosed photon energy range.

The selected photon energy absorption enhancer, the spectra of thephoton energy absorption enhancer, and the spectra of the photon energysource represent important aspects for achieving a desired overallheating performance. Referring to FIG. 2, an area-intersection (A3) ofthe photon energy absorption enhancer normalized absorbance (A1) spectraand the photon energy source's normalized emission spectra (A2) musthave at least some overlap to achieve improved photon energy absorptionand subsequent heating. In one aspect, the area-intersection of thephoton energy absorption enhancer normalized absorbance spectra and thephoton energy source's normalized emission spectra must be at least 10%of the area-under-the-curve for either the additive or the photon energysource. In another aspect, this area-intersect is at least 25%. Inanother aspect, this area-intersect (A3) is at least 50%.

In another aspect, one or more photon energy absorption enhancers isadded to the dental material at a concentration of about 0.001%-10% (wt%) to increase the photon energy absorption of the dental material. Inanother aspect, one or more photon energy absorption enhancers is addedto the dental material at a concentration of about 0.005%-7% (wt %). Inanother aspect, one or more photon energy absorption enhancers is addedto the dental material at a concentration of about 0.01%-3% (wt %). Inanother aspect, one or more photon energy absorption enhancers is addedto the dental material at a concentration of about 0.01%-1% (wt %). Inanother aspect, one or more photon energy absorption enhancers is addedto the dental material at a concentration of about 0.001%, about 0.005%,about 0.01%, about 0.05%, about 0.1%, about 0.2%, about 0.4%, about0.8%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about7%, about 8%, about 9%, or about 10% (wt %).

In another aspect, one or more photon energy absorption enhancers isadded to the dental material container at a concentration of about0.1%-25% (wt %) to increase the photon energy absorption of the dentalmaterial container. In another aspect, one or more photon energyabsorption enhancers is added to the dental material container at aconcentration of about 0.1%-20% (wt %). In another aspect, one or morephoton energy absorption enhancers is added to the dental materialcontainer at a concentration of about 0.1%-15% (wt %). In anotheraspect, one or more photon energy absorption enhancers is added to thedental material container at a concentration of about 0.1%-10% (wt %).In another aspect, one or more photon energy absorption enhancers isadded to the dental material container at a concentration of about0.1%-5% (wt %). In another aspect, one or more photon energy absorptionenhancers is added to the dental material container at a concentrationof about 0.1%-1% (wt %). In another aspect, one or more photon energyabsorption enhancers is added to the dental material container at aconcentration of about 0.1%, about 0.5%, about 1%, about 2%, about 4%,about 5%, about 7%, about 9%, about 11%, about 13%, about 15%, about17%, about 20%, or about 25% (wt %).

In another aspect, one or more thermal conductivity enhancers is addedto the dental material. Suitable thermal conductivity enhancers improvethe thermal conductivity of the material and/or the material'scontainer. This allows heat to more quickly disperse throughout thematerial and/or material's container, or improve the conductive transferof heat between the material and its container. Exemplary andnon-limiting additives to improve thermal conductivity include: graphiteparticles, graphene particles, ceramic particles (e.g. metal nitrides,boron nitride, silicon carbide, and silicon nitride), metal oxideparticles (e.g. aluminum oxides), metal particles, and carbon nanotubes.In another aspect, one or more thermal heating additives is added to thedental material at a concentration of about 0.01%-80% (wt %). In anotheraspect, one or more thermal heating additives is added to the dentalmaterial at a concentration of about 0.01%-50% (wt %). In anotheraspect, one or more thermal heating additives is added to the dentalmaterial at a concentration of about 0.01%-30% (wt %). In anotheraspect, one or more thermal heating additives is added to the dentalmaterial at a concentration of about 0.01%-10% (wt %). In anotheraspect, one or more thermal heating additives is added to the dentalmaterial at a concentration of about 0.01%-1% (wt %).

In another aspect, one or more thermal conductivity enhancers is addedto the dental material container. Suitable thermal conductivityenhancers improve the thermal conductivity of the material and/or thematerial's container. This allows heat to more quickly dispersethroughout the material and/or material's container, or improve theconductive transfer of heat between the material and its container.Exemplary and non-limiting additives to improve thermal conductivityinclude: graphite fibers, graphene flakes, ceramic particles (e.g. metalnitrides, boron nitride, silicon carbide, and silicon nitride), metaloxides (e.g. aluminum oxides), metal particles, and carbon nanotubes. Inanother aspect, one or more thermal heating additives is added to thedental material container at a concentration of about 0.01%-80% (wt %).In another aspect, one or more thermal heating additives is added to thedental material container at a concentration of about 0.01%-50% (wt %).In another aspect, one or more thermal heating additives is added to thedental material container at a concentration of about 0.01%-30% (wt %).In another aspect, one or more thermal heating additives is added to thedental material container at a concentration of about 0.01%-10% (wt %).In another aspect, one or more thermal heating additives is added to thedental material container at a concentration of about 0.01%-1% (wt %).

Additives for Improving Material Polymerization (Photoinitiator andCoinitiator)

In another embodiment, a photopolymerization enhancer system isincorporated into a photopolymerizable dental material composition. Theinclusion of such a system can improve polymerization, depth-of-cure,and degree-of-conversion using photon energy. The photopolymerizationenhancer system described herein is succinctly different from otherknown photopolymerization systems because it includes a type Iphotoinitiator and a type II photoinitiator with a coinitiator or twotype II photoinitiators with coinitiator(s), wherein at least one type Ior type II photoinitiator is activated photon energy in a suitablerange. In some aspects, the range of photon energy in which at least oneof the photoinitiators is activated is about 0.49 eV-2.38 eV (2500nm-520 nm), herein referred to as a “specified photoinitiator.”

In one aspect, the photopolymerization enhancer system includes a type Iphotoinitiator and a type II photoinitiator with at least onecoinitiator, wherein at least one or all of the photoinitiators is aspecified photoinitiator. In another aspect, the photopolymerizableenhancer system includes two type II photoinitiators with at least onecoinitiator, wherein one or all of the photoinitiators is a specifiedphotoinitiator. In another aspect, the coinitiator is present at aconcentration that is greater than or equal to the specifiedphotoinitiator. In another aspect, the coinitiator and the othernon-specified photoinitiator is present at a concentration that isgreater than or equal to the specified photoinitiator. In anotheraspect, the combination of the coinitiator and the other non-specifiedphotoinitiator is present at a concentration that is greater than orequal to the specified photoinitiator. In another aspect, at least oneof the coinitiators is borate V. In another aspect, the specifiedphotoinitiator is incorporated at a concentration of about 0.0001%-2% byweight of the total photopolymerizable dental material. In anotheraspect, the specified photoinitiator is incorporated at a concentrationof about 0.0001%-1% by weight of the total photopolymerizable dentalmaterial. In another aspect, the specified photoinitiator isincorporated at a concentration of about 0.0001%-0.5% by weight of thetotal photopolymerizable dental material.

In another aspect, the photopolymerization enhancer system includes atype I photoinitiator and a type II photoinitiator with at least onecoinitiator, or two type II photoinitiators with at least onecoinitiator, wherein the specified photoinitiator is incorporated at aconcentration of 0.0001%-0.5% by weight of the total photopolymerizabledental material, wherein the coinitiator(s) and the other photoinitiatoris present at a concentration greater than or equal to the specifiedphotoinitiator, wherein at least one of the coinitiators is borate V. Inanother aspect, the photopolymerizable enhancer system includes a type Iphotoinitiator and a type II photoinitiator with at least onecoinitiator, or two type II photoinitiators with at least onecoinitiator, wherein the specified photoinitiator is incorporated at aconcentration of 0.001%-0.1% by weight of the total photopolymerizabledental material, with at least one of the coinitiators is borate V thatis at least 10 times more concentrated than the specifiedphotoinitiator, and with the other photoinitiator at a concentrationgreater than or equal to the specified photoinitiator.

In another aspect, the specified photoinitiator or co-initiator added tothe photopolymerizable dental material is capable of losing its visiblecolor (i.e., it becomes bleached or colorless) as a result of theapplication of photon energy of between 0.49 eV-1.90 eV (2500 nm-650 nm)or 1.23 eV-2.06 eV (1000 nm-600 nm) and/or is consumed during thephotopolymerization process occurring after the application of photonenergy of between 0.49 eV-1.90 eV (2500 nm-650 nm) or 1.23 eV-2.06 eV(1000 nm-600 nm). During a clinical application, the photopolymerizabledental material (e.g., a dental composite) can start as a distinctcolor, and change to the desired tooth shade once it is cured. Thisproperty gives the clinician the benefit of visual confirmation of acompleted cure.

In another aspect, the specified photoinitiator absorbs photon energybetween 0.49 eV-1.90 eV (2500 nm-650 nm) and photobleaches or becomescolorless. In another aspect, the specified photoinitiator facilitatesmaterial curing via increased radical formation and simultaneouslybleaches as formed radicals deplete. Thus, in some aspects, thespecified photoinitiator participates in the curing process and providesa visible change to indicate complete curing. In these aspects, thespecified photoinitiator is used in conjunction with anotherphotoinitiator and/or co-initiators at the concentrations disclosedherein.

Exemplary and non-limiting type I photoinitiators that can be used inconjunction with the specified photoinitiator include: TPO(diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide),2-Benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophe-nyl)-butane-1-one(BDMB), 2,2-dimethoxy-2-phenylacetophenone (DMPA), Bis-acylphosphineoxide (BAPO), acyl germane derivatives, benzoin ethers, benzyl ketals,α-dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones,acylphosphine oxides, and fluorone dyes. Exemplary and nonlimiting typeII photoinitiators that can be used in conjunction with the specifiedphotoinitiator include: 1-phenyl 1,2-propanedione (PPD), camphoroquinone(CQ), ethyl-4-(dimethylamino)benzoate (EDB), benzil (BZ) and cyaninedyes. Additional suitable photoinitiators that may be used inconjunction with the specified photoinitiator include, but are notlimited to: acetophenones, titanocene, germane based compounds,benzophenone derivatives, dibenzoylferrocene, iridium complexes, pyrenederivatives, thiobarbituric acid derivatives, benzyl and benzoincompounds, benzophenones, thioxanthones, sulfoniums, iodoniums,peri-Arylenes (particularly sexterrylenes, specificallySexterrylenetetracarboxylic Bisimides), squaraines, phthalocyanines, andphthalocyanines metal complexes, polymethine cyanines, porophyrines,chlorines, benzochlorines, thiazines and a cyanin-based photoinitiatorshown as structure S1. Commercially available photoinitiators include,but are not limited to: photoinitiators from Spectra Group Limited, Inc.(H-Nu 660, H-Nu 780, H-Nu 815.

S1

Exemplary and nonlimiting classes of co-initiators that may be used withthe type I and specified photoinitiator, or the type II and specifiedphotoinitiator include: amine-based co-initiators (e.g.ethyl-4-dimethylaminobenzoate (DMABE), 4-dimethylamino benzonitril(DMABN), 2-N,N-dimethylamino ethyl methacrylate (DMAEMA) or otherpyridinium-based compounds), borate-based co-initiators (e.g.,butyltriphenylborate referred to as borate V, tetrabutylammoniumtetrafluoroborate), and iodonium salts. Commercially availableco-initiators include, but are not limited to: co-initiators fromSpectra Group Limited, Inc. (e.g., borate V, H-Nu 254, which is aniodonium salt).

Additives for Improving the Material's Reactivity (Photocatalyst)

Another embodiment includes a method for improving the reactivity of adental material by including one or more photocatalysts. Theincorporation of a photocatalyst is thought to absorb the applied photonenergy and acts as a photocatalyst to enhance other dental materialproperties. Exemplary and non-limiting photocatalysts include those suchas metal oxides. A potential application of this photocatalyst is toplace a metal oxide within an endodontic irrigant or oral rinse andsubject it to photon energy for improved disinfection.

Methods for Treating a Patient with a Dental Material

Another embodiment described herein is a method of treating a patientwith a dental material comprising heating the dental material aboveambient temperature with a device using photon energy from a photonenergy emission source and applying the heated dental material to asurface of the tooth or a tooth cavity, prior to curing of the material(if applicable, i.e. prior to curing of dental photopolymerizablematerials).

As described herein, the photon energy comprises an energy of about 0.49eV-2.38 eV (2500 nm-520 nm) or about 1.23 eV-2.06 eV (1000 nm-600 nm).In one aspect, the dental material is a dental photopolymerizablematerial. In another aspect, the emitted photon energy, which heats thedental material, does not prematurely cure or cause the material topolymerize and is at a suitable absorption wavelength of the dentalmaterial, a dental material container, or a heating additive describedherein.

The dental photopolymerizable material includes composite resins, highlyfilled composite resins, glass ionomer resins, sealants, cements, cavityliners, or combinations thereof. Following application of the heateddental material, the method for treating a patient further includescuring the dental material. In one aspect, the curing further includesapplying a second source of photon energy with an absorption spectra ofa photopolymerizable material that is present in the dental material toinitiate polymerization. Thus, in this aspect, during the treatment of apatient, an applied photon energy for heating the dentalphotopolymerizable material does not overlap with an absorbance of aphotoinitiator present in the dental photopolymerizable material.

Device for Heating and Dispensing Dental Materials

The inventive devices described herein allow for the creation of dentalcomposites with higher filler content. Higher filler content is desiredas it leads to less shrinkage during curing and harder, more wearresistant, and longer lasting restorations. However, highly filledcomposite is limited in use due to its low flowability, high extrusionforce for dispensing, and poor shaping ability, leading to poor marginaladaptation. Preheating the photopolymerizable materials lowers theviscosity and reorders the molecular structure of the filler and monomerreducing internal stresses and heterogeneity thereby improving clinicaluse of highly filled composites. Additionally, preheatingphotopolymerizable materials and curing at an elevated temperatureincreases volumetric expansion of the composite (i.e. thermal expansion)which can offset the volumetric reduction caused by polymerization. Thissignificantly reduces composite shrinkage, leakage, stresses, andpost-operative pain.

Thus, another embodiment is a device capable of emitting photon energybetween 0.49 eV-2.38 eV (i.e. 2500 nm-520 nm) can be used to heat and/ordispense dental materials. In one aspect, the utilized photon energy isbetween 1.23 eV-2.06 eV (1000 nm-600 nm) or 1.23 eV-1.77 eV (i.e. 1000nm-700 nm) to heat and dispense dental materials as the applied photonenergy is invisible to the human eye and safer. The photon energy sourceis limited to an electroluminescence source, such as a light emittingdiode (LED) or a laser diode, and provides optical power between 0.5 Wand 20 W or between 1 W and 8 W.

Suitable devices described herein may be cordless and furthermoreincorporate a rechargeable energy source, such as a lithium ion battery,super capacitor, lithium polymer battery, nickel cadmium battery, ornickel metal hydride battery. In another aspect, the device includes acompule or container having a dental material therein. The compule canbe removed from the device after application of the dental material andreplaced with another compule or container for a subsequent applicationin the same or a subsequent procedure.

In another aspect, the photon energy source is arranged in closeproximity to the compule or container to ensure efficient energytransfer. In another aspect, the distance between the photon energysource and compule or container is less than one centimeter.Alternatively, in another aspect, the photon energy source is collimatedvia a lens or fiber optic to ensure higher energy transfer to thecompule or container and/or allow the photon energy source to be locatedat a greater distance from the compule or container.

In another aspect, the tool or wand effectively thermally manages thephoton energy source in order to keep the device from elevated thermaltemperatures that can degrade the dental material or is dangerous to anoperator of the device or a patient being treated with the device. Thiscan be accomplished by placing the photon energy source on a primaryheat sink, such as a printed circuit board or a metal clad printedcircuit board, which may be further coupled to a secondary or tertiaryheat sink, which may be contained within the device housing or maycomprise the device housing. Additionally, the use of a heat pipe canhelp facilitate thermal management. Through proper thermal managementthe device body, and touchable surfaces, should not reach unsafeelevated temperatures, which are commonly defined as temperatures aboveapproximately 50° C. for medical devices.

In another aspect, to minimize the negative impacts of excessive orundesirable temperatures occurring to the dental materials, the deviceincludes a sensor to control the applied photon energy. A temperaturesensor can be used to monitor the temperature of the dental materialwithin the tool/wand during the application of photon energy and/ordetermine when the object is at a desired temperature and feedback thisinformation to the applied photon energy source to reduce or remove thepower output of the emitter as detailed in the block diagram illustratedin FIG. 37. Exemplary and non-limiting temperature sensors include athermistor, IR temperature sensor, thermopile, thermocouple, or aresistance temperature detector (RTD). The temperature sensor can alsobe part of the object that is being heated instead of being part of thedevice. This can be done by embedding a thermistor on the object ormaking the object out of a material that changes its electricalproperties (i.e. resistance, capacitance, or inductance) in relation toits change in temperature, and then by making an electrical connectionwith the device. Suitable temperature sensors are available from VishayDale (TFPT), Panasonic (AMG88), Texas Instruments (TMP007), Digilent,Inc. (240-080), and TE Connectivity (Ni1000SOT).

Furthermore, it is envisioned that once the object reaches the desiredtemperature, the device can use pulse-width modulation (PWVVM),proportional-integral-derivative controller (PID), or another controlloop feedback system approach to maintain the desired temperaturewithout reaching undesirable temperatures which can have a negativeimpact on the dental material. Furthermore, in lieu of or in addition toa temperature sensor, another sensor can be used to determine howabsorbing the object is and adjust power to the photon energy sourceaccordingly to account for differences in the dental materialsabsorbance and required power and on time to reach a desiredtemperature. This can be achieved with a thermopile, RGB sensor,proximity sensor, phototransistor, photodiode, ambient light sensor,CMOS sensor, or CCD sensor to either directly or indirectly determinethe absorption or color of the object for a specific wavelength ofphoton energy, either by measuring reflectance or transmittance.Suitable sensors are available from Vishay Semiconductor (VCNL4020X01,VEML6040), Rohm Semiconductor (BH1680FVC), Texas Instruments (TMP007),Everlight Electronics Co Ltd (PD15-22C/TR8), Kingbright (APA3010P3BT),OmniVision Technologies Inc. (OV09740-A46A), and Toshiba (TCD1103GFG).

In addition, the same sensor used for determining absorption, or aseparate implementation of one of the aforementioned sensor, can beimplemented so that the device only works with a manufacturer's specificobject or container or material, as the sensor's measured value canserve as a “fingerprint” to identify the inserted object or container ormaterial to implement a closed platform system. This would allowmanufacturers to ensure only their product is heated using this device.Furthermore, as a safety feature, the device can incorporate using anyof the above mentioned sensors to determine if the object is presentprior to starting or during heating, such that photon energy is onlyemitted when an object is present.

According to another aspect, the device used for heating and dispensingincludes a curing light source at 365 nm-500 nm and an additional sourceof photon energy between 0.49 eV-2.38 eV (i.e. 2500 nm-520 nm), between1.23 eV-2.06 eV (1000 nm-600 nm), or between 1.24 eV-1.77 eV (i.e. 1000nm-700 nm) that can be activated and directed at the composite afterapplication of the composite in order to heat and/or cure the compositewhere applied. Both the curing light source and photon energy sourcewould each emit between an optical power of between 500 mW and 3 W orbetween 700 mW and 1.5 W of optical power. In another aspect, the photonenergy can be applied prior, simultaneously, or after a short delay ofabout a couple seconds compared to the curing light source to modulatethe resultant dental composite properties. The photon energy can bedirectly absorbed by the composite material (i.e. constituents withinthe composite material such as monomers and fillers, or incorporatedadditives), or an additive to the composite material to heat the dentalmaterial during curing with one of the aforementioned additives that mayalso be used for heating prior to curing.

In another aspect, the curing light and photon energy sources arearranged distally on the device to facilitate access in the oral cavity.Alternatively, in another aspect, the curing light and/or photon energysource can be collimated via a lens or fiber optic to ensure higherenergy transfer to the placed material and/or allow the curing andphoton energy sources to be located at a non-distal position in thedevice. The device effectively thermally manages the curing light andphoton energy sources in order to keep the device from elevated thermaltemperatures, which degrades the dental composite material or isdangerous to an operator of the device or a patient being treated withthe device. This can be accomplished by placing the photon energy sourceon a primary heat-sink (a printed circuit board or a metal clad printedcircuit board), which may be further coupled to a secondary or tertiaryheat-sink, which may be contained within the device housing or maycomprise the device housing/body. Additionally, the use of a heat pipecan help facilitate thermal management. Clinically, the use of thedisclosed photon energy device and method can improve surface hardness,degree of conversion, depth of cure, reduce shrinkage and leakage, andcan be used to improve incremental layering and curing of restorationmaterial improving procedural efficiency. In another aspect, this canalso be accomplished with a separate device that does not dispense thedental material and would be restricted to curing photopolymerizablematerials, i.e. a multispectral curing light.

One embodiment described herein is a device according to any one of FIG.14-16 or 28-32. In one aspect, the device has a package of photonemitters according to any one of FIG. 17-19 or 35.

Device for Enhancing the Cure of Photopolymerizable Dental Materials

According to another embodiment of the invention, a tool or wand can usephoton energy to heat the photopolymerizable dental material aboveambient temperature and cure the photopolymerizable dental material.This results in curing of the photopolymerizable dental material at anelevated temperature in situ and/or in vivo which has significantbenefits to the mechanical properties of the photopolymerizable dentalmaterial. In one aspect, this device has a thermally conductive body,and in another aspect, this device is elongated to facilitate easyaccess in the mouth. Additionally, the device includes at least fourdiscrete distally mounted photon energy emission sources that produce atleast two discrete emission spectra. In one aspect, these photon energyemission sources consist of light emitting diodes (LEDs). At least oneLED emission spectra is used for curing the photopolymerizable dentalmaterial, and at least one LED emission spectra is used to elevate thephotopolymerizable dental material's temperature above ambient prior toor during curing. In one aspect, the emission source for curing thephotopolymerizable dental material emits light between 365 nm-500 nm,and at a power between 500 mW and 3 W of optical power. In anotheraspect, the emission source for curing the photopolymerizable dentalmaterial emits light between 420 nm-490 nm, and at a power between 700mW and 1.5 W of optical power. In another aspect, the emission sourcefor elevating the photopolymerizable dental material's temperature aboveambient temperature during curing emits light between 520 nm-2500 nm,and at a power between 500 mW and 3 W of optical power. In anotheraspect, the emission source for elevating the photopolymerizable dentalmaterial's temperature above ambient temperature during curing emitslight between 600 nm-1000 nm, and at a power between 700 mW and 2 W ofoptical power.

It was discovered that the spatial orientation of these at least fourLEDs ensures a near uniform beam profile, such that optical power doesnot vary considerably throughout the illumination field. In one aspect,one LED is centrally located within the distal head of the device, andat least three LEDs are located radially about the centrally locatedLED. These at least four LEDs can be located on the same PCB or separateparallel PCBs (see FIGS. 17-19 and 35), and may be located on the sameplane or separate parallel planes. However, in another aspect, the atleast four LEDs emit their beam profiles in generally the same directionso the beam profiles can be collimated to provide an even illuminationfield. Furthermore, if more than three radially spaced LEDs are to beincorporated, the spacing (i.e. angular separation) between LEDs shouldbe equal for uniform beam profile. For example, three LEDs should beangularly separated by about 120° (see FIGS. 17 and 35), four LEDsshould be angularly separated by about 90°, and five LEDs should beangularly separated by about 72°. In another aspect, one centrallylocated LED is contained on its own PCB, which is surrounded by threeLEDs contained on a separate PCB, wherein the three LEDs are placed onthe same plane 120° apart.

Depending on the clinical procedure, the various LEDs may have differentemission output powers and durations themselves or respect to oneanother. For example, the output of the centrally located LED may lead,lag, or is simultaneously used with the output of the at least threeradially located LEDs. If the clinician wanted to soften and/ormanipulate the photopolymerizable dental material in situ and/or in vivothe device may incorporate a setting that only illuminates thephotopolymerizable dental material to elevate the material'stemperature, which subsequently decreases the material's viscosity. Atthis point, the material can be manipulated to the desiredshape/structure prior to curing. Alternatively, elevating thephotopolymerizable dental material's temperature in situ and/or in vivo,without physical manipulation, is also possible and would beadvantageous to decrease its viscosity and improve conformation to thetooth surface. The heated photopolymerizable dental material can then becured in situ and/or in vivo at an elevated temperature while it is mostconformed to the tooth surface. An example setup to achieve thissituation would be to illuminate the photopolymerizable dental materialwith the spectrum of 520 nm-2500 nm to elevate its temperature for about5 to about 30 seconds immediately prior to illuminating thephotopolymerizable dental material with the spectrum of 365 nm-500 nm tocure for about 3 to about 30 seconds. In one aspect, the device has 2-5different preprogrammed settings for various clinicalprocedures/preferences, wherein each mode has differing power, duration,and overlap characteristics of the at least two emission spectrums,wherein at least one emission spectra is within the specified photonenergy range.

In another aspect, to ensure proper thermal management of the photonenergy emission sources (e.g. LEDs), the photon energy emission sourcesis coupled to a primary heat sink located within the device. In anotheraspect, these primary heat sinks are coupled to the thermally conductivebody. Alternatively, in another aspect the primary heat sink for the atleast three radially located LEDs may be coupled to the primary heatsink of the centrally located LED, which is then coupled to thethermally conductive body. Lastly, in another aspect, these photonenergy emission sources are in electrical communication to a directcurrent power source. In another aspect, this direct current powersource is a detachable, rechargeable power source, such as a lithium ionbattery.

Optionally, other dental devices can be incorporated within thismultispectral curing device, which may include, but is not limited to: atransilluminator.

Another embodiment is a device according to any one of FIGS. 33-34. Inone aspect, the device has a package of photon emitters according to anyone of FIGS. 17-19 and 35.

Compositions of Dental Materials and Containers

Another embodiment is a dental material composition. In some aspects,the dental material is a photopolymerizable dental material composition.The dental material compositions described herein have enhanced energyconversion efficiency, heat transfer, and/or polymerizationcharacteristics.

In some aspects the photopolymerizable dental material compositionsdescribed herein include: acrylate monomers (e.g., triethylene glycoldimethacrylate, TEGDMA, urethane dimethacrylate, UDMA, andbisphenol-A-glycidyldimethacrylate, bis-GMA, etc), inorganic fillers(e.g., glasses or ceramics, i.e., silicon dioxide, crystalline silica,borosilicate glass, zirconium oxide, zirconia-silica, etc),photopolymerization systems (e.g., camphoroquinone with amine-basedco-initiators), and optionally one or more pigments or colorants tomatch tooth color, and optionally one or more heating additives,optionally a polymerization enhancer system and optionally one or morethermal conductivity enhancers. As described herein, the heatingadditive, polymerization enhancer system, and thermal conductivityenhancers improve the material's energy conversion efficiency, heattransfer properties, and/or polymerization.

In one aspect, the dental material composition includes about 1% toabout 40% by weight of acrylate monomers. In another aspect, the dentalmaterial composition includes about 5% to about 30% by weight ofacrylate monomers. In another aspect, the dental material compositionincludes about 5% to about 20% by weight of acrylate monomers. Inanother aspect, the dental material composition includes about 5% toabout 15% by weight of acrylate monomers. In another aspect, the dentalmaterial composition includes about 1%, 5%, 10%, 15%, 20%, 25%, 30%,35%, or 40% by weight of acrylate monomers.

In another aspect, the dental material composition includes about 30% toabout 95% by weight of an inorganic filler. In another aspect, thedental material composition includes about 60% to about 95% by weight ofan inorganic filler. In another aspect, the dental material compositionincludes about 5% to about 20% by weight of an inorganic filler. Inanother aspect, the dental material composition includes about 5% toabout 15% by weight of an inorganic filler. In another aspect, thedental material composition includes about 1%, 5%, 10%, 15%, 20%, 25%,30%, 35%, or 40% by weight of an inorganic filler monomers.

In some aspects, the heating additive, polymerization enhancer systemand thermal conductivity enhancer is provided into the dental materialcompositions described herein at the concentrations described by theembodied methods above.

An exemplary embodiment of the photopolymerizable dental material isdisclosed in tables 1-2. This exemplary dental material compositionincludes an absorbing dye (e.g., LUNIR1) as a photon energy absorptionenhancer to significantly increase the heating of the material. Asdescribed herein additional heating additives and/or polymerizationenhancers may be added to the disclosed composition to further enhancethe material's energy conversion efficiency, heat transfer properties,and/or polymerization characteristics. Alternatively, other additivesmay be incorporated to tailor the material's absorption properties toany photon energy in the disclosed photon energy range.

TABLE 1 Exemplary Photopolymerizable Dental Material Composition Havinga Photon Energy Absorption Enhancer Concentration range Exampleconcentration Constituent (%) (%) Acrylate monomers    5-30% 13.89%Inorganic fillers    60-95% 85.00% Camphorquinone  0.001-0.5% 0.05%photoinitiator Amine-based co-initiator(s) 0.001-1% 0.10% Hydroquinone(stabilizer) 0.0001%-0.05% 0.01%

TABLE 2 Exemplary Photopolymerizable Dental Material Composition Havinga Photon Energy Absorption Enhancer Concentration range Exampleconcentration Constituent (%) (%) Acrylate monomers    5-30% 13.89%Inorganic fillers    60-95% 84.90% Photoinitiator(s)  0.001-0.5% 0.10%Co-initiator(s) 0.001-1% 0.20% Stabilizer 0.0001%-0.05% 0.01% Heatingadditive 0.001%-10%  0.90%

A further exemplary embodiment is provided in table 3. This exemplarydental material composition includes a photopolymerization enhancersystem including two type II photoinitiators (camphoroquinone and H-Nu660; of which H-Nu 660 is the specified photoinitiator as describedherein) and another co-initiator (borate V) to significantly increasepolymerization the material. This composition also results in aformulation that changes color from “blue/green” to “tooth shade,” whichprovides confirmation to the clinician that the composite issufficiently cured (see FIG. 27). As described herein additional heatingadditives and/or polymerization enhancers may be added to the disclosedcomposition to further enhance the material's energy conversionefficiency, heat transfer properties, and/or polymerizationcharacteristics. Alternatively, other additives may be incorporated totailor the material's absorption properties to any photon energy in thedisclosed photon energy range.

TABLE 3 Exemplary Dental Material Composition Having aPhotopolymerization enhancer system Concentration range Exampleconcentration Constituent (%) (%) Acrylate monomers   5-30% 17.845% Inorganic fillers  60-95%  85% Camphoroquinone 0.001-0.5% 0.05%photoinitiator Amine-based co-initiator(s) 0.001-1%  0.05% H-Nu 660photoinitiator 0.001-0.5% 0.005%  Borate V co-initiator 0.01%-5%   0.05%

Another exemplary composition is provided in table 4. This exemplarydental material composition includes a dental composite materialcomprising two type II photoinitiators (camphoroquinone and H-Nu 660; ofwhich H-Nu 660 is the specified photoinitiator as described herein) anda co-initiator (borate V) to significantly increase polymerization thematerial. This composition also results in a formulation that changescolor from “blue” to “tooth shade”, which provides confirmation to theclinician that the composite is sufficiently cured. As described hereinadditional heating additives and/or polymerization enhancers may beadded to further enhance the material's energy conversion efficiency,heat transfer properties, and/or polymerization characteristics.Alternatively, other additives may be incorporated to tailor thematerial's absorption properties to any photon energy in the disclosedphoton energy range.

TABLE 4 Exemplary Dental Material Composition Having aPhotopolymerization enhancer system Concentration range Exampleconcentration Constituent (%) (%) Acrylate monomers   5-30% 14.895%Inorganic fillers  60-95% 84.95% Camphoroquinone 0.001-0.5% 0.05%photoinitiator H-Nu 660 photoinitiator 0.001-0.5% 0.005% Borate Vco-initiator 0.01%-5%   0.1%

A further example of a photopolymerizable composition utilizing aphotoinitiator system described herein is provided in tables 5-6, whichare formulations for a dental sealant.

TABLE 5 Exemplary Photopolymerizable Dental Sealant Composition Having aHeating Additive Concentration range Example concentration Constituent(%) (%) Acrylate monomers  40-90% 88.885%  Inorganic fillers   1-20% 10% Photoinitiator 0.001-0.5% 0.05% Additional photoinitiator0.001-0.5% 0.005%  Stabilizer 0.0001%-0.05%  0.01% Co-initiator(s)0.001-1%  0.05% Heating additive 0.001%-10%     1%

TABLE 6 Exemplary Photopolymerizable Dental Sealant Composition Having aHeating Additive Concentration range Example concentration Constituent(%) (%) Acrylate monomers    40-90% 88.89%  Inorganic fillers    1-20% 10% Photoinitiator  0.001-0.5% 0.05% Stabilizer 0.0001%-0.05% 0.01%Co-initiator(s) 0.001-1% 0.05% Heating additive 0.001%-10%    1%Endodontic Filling Materials

Another embodiment, is a composition for dental materials, specificallyendodontic filling materials such as gutta percha, which displayenhanced energy conversion efficiency and/or heat transfercharacteristics.

In one aspect, the disclosed composition for gutta percha endodonticfilling includes the following constituents: gutta-percha or otherpolyisoprene derivatives, inorganic fillers (glasses or ceramics, e.g.zinc oxide, titanium oxide, silicon dioxide, crystalline silica,borosilicate glass, zirconium oxide, zirconia-silica, etc), aradiopacifier (e.g., barium sulfate, bismuth sulfate, tungsten),stabilizer(s) (e.g. antioxidants, butylated hydroxytoluene), waxes orresins (e.g., metal stearate complexes, zinc stearate, polyethyleneglycol, paraffin wax, palmitates, carnauba wax, etc) and at least oneheating additive to improve the material's energy conversion efficiencyand/or heat transfer properties. These heating additives will beincorporated into the dental material (e.g. gutta percha) atconcentrations described herein.

Another exemplary composition is provided in tables 7-8. This exemplarygutta percha endodontic filler dental material composition includes anabsorbing dye (i.e., indocyanine green) as a photon energy absorptionenhancer to significantly increase the heating of the material.Additional additives may be added to the disclosed composition tofurther enhance the material's energy conversion efficiency and/or heattransfer properties. Alternatively, other additives may be incorporatedto tailor the material's absorption properties to any photon energy inthe disclosed photon energy range.

TABLE 7 Exemplary Gutta Percha Dental Material Composition Having aPhoton Energy Absorption Enhancer Concentration range Exampleconcentration Constituent (%) (%) Gutta percha 10-30% 23% Inorganicfiller 60-85% 60% Radiopacifier 1.0-30%  12% Wax(es) and resin(s)0%-10%   3% Heating additive 0.01%-10%      2%

TABLE 8 Exemplary Gutta Percha Dental Material Composition Having aPhoton Energy Absorption Enhancer Concentration range Exampleconcentration Constituent (%) (%) Gutta percha 10-30% 15% Aluminumnitride 50-85% 60% Barium sulfate 1.0-35%  20% Paraffin 0%-10%   3%Indocyanine green 0.001%-10%     2%Dental Material Housing

Another embodiment, is a dental material container, which displaysenhanced energy conversion efficiency and/or heat transfer whenirradiated with the disclosed photon energy.

The disclosed composition for dental material containers includes thefollowing constituents: a thermoplastic resin (e.g. polycarbonate,polyamide, polypropylene, polyethylene, etc), and at least one additiveto improve the material's energy conversion efficiency and/or heattransfer properties. The composition may also include colorants or otherpigments, plasticizers, or other fillers (e.g. glass fibers, carbonblack, etc.). With regard to photopolymerizable dental materials, suchas a dental composite, the additive, colorant, pigment, or other fillershould sufficiently block polymerization light from transmitting throughthe container to the composite, which would cure the photopolymerizablematerial inside the container.

Example compositions for a dental material's container are described intables 9-14. The following tables below detail container formulationsincorporating a heating additive to significantly increase the heatingrate and overall temperature change of the material located within.

TABLE 9 Exemplary Dental Material Container Having a Heating AdditiveConcentration range Preferred concentration Constituent (%) (%)Thermoplastic resin   50-99.9% 95% Heating additive 0.1-50%   5%

TABLE 10 Exemplary Dental Material Container Having a Photon EnergyAbsorption Enhancer Heating Additive Concentration range Preferredconcentration Constituent (%) (%) Polycarbonate   50-99.9% 95% Epolight7657 0.1-50%   5%

Additional additives can be added to the above compositions to furtherenhance the material container's energy conversion efficiency and/orthermal transfer properties. These additives would be incorporated atconcentrations disclosed below. For example, boron nitride can be addedto the composition to increase heat transfer properties of thecontainer.

TABLE 11 Exemplary Dental Material Container Having Multiple HeatingAdditives Concentration range Preferred concentration Constituent (%)(%) Thermoplastic resin  50-99.9% 92%  Heating additive 1 0.1-50% 5%Heating additive 2 0.01%-20%    3%

TABLE 12 Exemplary Dental Material Container Having a ThermalConductivity Enhancer and Photon Energy Absorption Enhancer HeatingAdditives Concentration range Preferred concentration Constituent (%)(%) Polycarbonate  50-99.9% 85% Epolight 7657 0.1-50%  5% Boron nitride0.01%-20%    10%

Alternatively, other additives can be used to tailor the container'sabsorption properties to any photon energy in the disclosed photonenergy range. Furthermore, other fillers can be added to enhance thematerial container's characteristics. For example, glass fibers can beadded to increase the container's strength.

TABLE 13 Exemplary Dental Material Container Having Multiple HeatingAdditives and a Filler Concentration range Preferred concentrationConstituent (%) (%) Thermoplastic resin   50-99.9% 71% Heating additive1 0.1-50%  7% Heating additive 2 0.01%-20%   12% Filler 1%-20% 10%

TABLE 14 Exemplary Dental Material Container Having Multiple HeatingAdditives and a Filler Concentration range Preferred concentrationConstituent (%) (%) Polycarbonate   50-99.9% 74% Epolight 7657 0.1-50% 1% Boron nitride 0.01%-20%   15% Glass fibers 1%-20% 10%

Another embodiment is a process for making the dental containerdescribed herein that includes a thermoplastic resin and a heatingadditive. In one aspect, the method includes the process of heating athermoplastic resin to at least its softening point. In another aspect,the method further includes maintaining and controlling the resintemperature to at least its softening point. In another aspect, themethod further includes adding an additive at about 0.1-5%. Suitableadditives include those, which have a high photon energy absorbancebetween 520 nm-2500 nm. In another aspect, the method includes whileadding an additive and optionally a dispersant the temperature of theresin is maintained at its softening point. In another aspect, themethod includes mixing and homogenizing a mixture containing the resin,additive, and optional dispersant while maintaining temperature to atleast the resin's softening point. In another aspect, the methodincludes extruding a homogenized mixture that contains the resin,additive, and optional dispersant into a mold cavity including thedental material container shape and allowing it to cool prior to removalfrom the cavity. Alternatively, in another aspect, a homogenized andheated mixture containing the resin, additive, and optional dispersantis formed into pellets, which can be later used for injection molding adental material container.

Another embodiment is a dental material container made by the processdescribed above. The formed dental material container is suitable forbeing filled with a dental material. Further, the formed dental materialcontainer made by the process above and containing a dental material issuitable for being heated with photon energy to quickly heat a dentalmaterial as described herein.

EXAMPLES Example 1 Application of Photon Energy to Anesthetic,Gutta-Percha, Dental Composite and Dental/EndodonticIrrigants—Absorbance and Performance

The benefits of the disclosed embodiments can be derived from theapplication of photon energy of dental materials including, but notlimited to: anesthetic (reducing pain during injection), gutta-Percha(for endodontic root canal obturation), dental composites, sealants,cements, cavity liners, and glass ionomer resins (e.g., loweringviscosity, improving handling characteristics, decreasing voids, andimproving mechanical properties post-cure) and endodontic irrigants(increasing efficacy and reactivity). For example, in FIG. 3, theabsorbance of three composite materials, i.e., Filtek Supreme Ultra,Spectrum TPH3 and Esthet.X HA, is compared with that of acrylic, andillustrates that 3 leading composite brands show similar absorptions toacrylic material. This indicates that the primary composition of dentalcomposite is the acrylic monomer, and that this is the primary structureattributing to its absorption, allowing for a particular wavelength bandto be selected, corresponding to overtone bands, for heating the acrylicmonomers and oligomers within the composite.

In addition, for dental materials including gutta purcha, which has thefollowing structure:

the targeted bond(s) for absorption and heating using near infrared IRphotons in gutta-percha—is the terpene molecule, which has C—C singlebonds and C—C double bonds. This is also clearly illustrated in FIG. 4which illustrates the peaks for the various bonds and molecules ingutta-percha and a highly filled composite material, e.g., Esthet.X HA,that can be targeted for near IR application and heating. In addition,separate from the material(s) forming the composite, thecomposite/dental material container, or compules, can be designed withspecific materials, additives, and/or colors with either low absorptionthat passes all photon energy to the composite or dental materialtherein, or high absorption to heat the compule/material containeritself. As shown in FIG. 5, different absorption characteristics areobtained for an identical plastic material (polycarbonate) of differentcolors/opacities. Any of these provided absorbance/overtone bands can betargeted for heating of dental materials and/or dental materialcontainers using photon energy.

Referring now to FIGS. 6 and 7, the ability to target the compositeand/or the compule with photon energy also provides a significantdecrease in the time required to heat the composite to the desiredtemperature. In other words, the use of photon energy provides asignificant increase in heating rate without any deleterious effects.For comparison, as shown in FIG. 6, heating a composite in acommercially available composite warmer is slow and reaches about 60° C.in 10 minutes. In contrast, as shown in FIG. 7, photon energy can beused to heat the same composite to the same temperature (60° C.) inunder 20 seconds, which is highly advantageous to the clinician as thissignificantly reduces procedural time and increases in-officeefficiencies. Different composites (and other dental materials) willheat up faster based on the composition of the composite itself, thecomposition of the material container, and/or the heat transferproperties of the composite or container. These same concepts hold truefor all dental materials. Heating time and rate is also related to thequantity and spatial orientation of the photon energy sources, i.e. asingle emitter with 4 W of power will be effective, but will not be asefficient as four emitters with 1 W of power each orientated around thecomposite container circumferentially. In a preferred embodiment of theinvention, a device is created which utilizes between 1 and about 6light emitting diodes to heat dental materials between about 60° C. and80° C. in between about 10 seconds and 60 seconds.

Example 2 Determination of Dental Material Viscosity at ElevatedTemperature

One additional consideration is the desired target temperature forheating the composite material and/or dental material, as thisdetermines the types and amount of photon energy required to achieve thedesired handling and/or performance characteristics. Additionally, forphotopolymerizable dental materials, the photon energy must not be inexcess, which may prematurely cure the photopolymerizable dentalmaterial prior to application. In one exemplary embodiment, thecomposite can be heated to a temperature between about 50° C. and about100° C., and more preferably 60° C. and about 80° C.

To determine this with more specificity the following evaluation (FIG.8) was undertaken:

Methods:

The rheological characterization of the four preheated resin basednanocomposite [Herculite Ultra (Kerr, Orange, Calif.), Tetric EvoCeram(Ivoclar Vivadent, Schaan, Liechtenstein), Filtek Supreme Ultra (3M, St.Paul, Minn.) and Grandio (Voco, Cuxhaven, Germany)] were carried outusing a shear rheometer with environmental control (Kinexus, Malvern,UK) using a stainless steel parallel-plate geometry setup (diameter of20 mm). The composite samples (0.2 g) were placed on the rheometer'slower plate, and the upper plate was lowered until it gently touched thesurface of the sample at a gap distance of 0.5 mm. The rheometer was setto various temperatures (25° C., 37° C., and 60° C.) and a delay of fiveminutes was employed prior to measurements to ensure the composite wasat the designated temperature. The shear rate was increased linearly inramp mode from 0.1 to 10 s⁻¹.

Results:

The results demonstrate that viscosity decreases by increasing the shearrate. Also, for all shear rates tested, viscosity varies as a functionof the heating temperature in the following order: 60° C.<37° C.<25° C.

Conclusion:

Regardless of the resin composite material used, it was found thatpreheating the dental nanocomposites considerably improves theirflowability, which provides increased mechanical bond and seal strength.Thus, increasing the shear rate and temperature resulted in asignificant decrease in shear viscosity

In addition, similar evaluations were performed on two additionalcomposites as shown in FIG. 8. As a result of these evaluations, it isseen that a benefit of heating highly filled composite is that it willbehave like a flowable composite at a certain temperature. Thistemperature can vary depending on the specific composite brand, howeverthe highly filled composite should be heated above about 60 C to achievedesired flowability. For even higher filled composites, this targettemperature is expected to be higher, perhaps about 70° C. or about 80°C. Regardless of the product, photon energy can be used to enhanceperformance and handling characteristics, such as flowability.Flowability aids in placement in the tooth, and highly filled compositeis more durable than flowable composite

Example 3. Effects of Temperature on Dental Materials

It is in some aspects, it is undesirable to heat the composite to atemperature at which the composite material will cure or harden. Forexample, at temperatures above 140° C. some dental composite will startto harden (either due to self-curing/polymerizing or evaporation ofconstituents) making it clinically unusable. This temperature will varydepending on the dental composite's composition, and some compositeshave maintained integrity at 200° C. This experiment is summarizedbelow.

Methods:

Dental composite from three manufacturers and Gutta Percha from onemanufacturer (3 samples of each) were placed on a hot plate and broughtup to 60° C. Temperature was monitored with a thermocouple placed in thecomposite. Temperature was raised by 5° C. every 3 minutes up until 150°C. After 150° C., temperature was raised by 10° C. every 3 minutes. Ametal spatula was used to probe the samples and observations wererecorded.

Results:

At 60° C., the composite viscosity was greatly reduced for all threebrands, supporting previous data. The gutta percha was very soft butstill viscous. By 115° C. the gutta percha became similar to thecomposite at 60° C. and was easy to manipulate with the spatula but hada stringy behavior. At 130° C. the gutta percha's stringinessdisappeared and the viscosity was significantly reduced and easilymalleable. By 140° C., two of the three composite brands started toharden. When removed from the hot plate, two hardened composites easilycrumbled when manipulated with little pressure. The third brand ofcomposite did not harden or crumble up to 200° C. It did not seem to beaffected, and was still able to be cured at this temperature. The guttapercha seemed unaffected up to 200° C. Between 200° C. and 250° C. itstarted to create a visible and odorous fume, but did not discolor ornoticeably change its material properties.

Conclusion:

Composite should be kept to temperatures below 140° C. to avoidcompromising performance, higher than 100° C. should not be clinicallyrequired since the desired flowability is already reached attemperatures <100° C. Gutta percha should not be heated above 200° C.;desired flowability is also reached below this temperature at about 115°C. to about 200° C. These temperature boundaries are considered in thisinvention. In some aspects, the use of photon energy does not increasethe temperature of dental materials greater than about 200° C. In someaspects, the use of photon energy does not increase the temperature ofdental materials greater than about 140° C.

In a different benchtop test (data not provided), a heat block and ovenwere brought to elevated temperatures of 120° C. and 150 degrees Celsiusto determine if primarily conductive heating from a very hot element canreduce the warm up time of a dental composite and compule. The compositereached 80° C. in over 30 seconds, but quickly continued to elevate intemperature >100° C. and hardened, rendering the material unusable. Thisdata supports that conductive heating, similar to commercially availablecomposite warming units, is unable to quickly warm the composite in asafe and controlled manner without deleterious effects on the composite.

Dental irrigants, such as ones containing sodium hypochlorite, haveenhanced performance at elevated temperatures (up to 60° C.) but alsodegrade quicker at higher temperatures and should not be heated aboveboiling (100° C.). Therefore, in one embodiment photon energy is used toheat dental liquids/irrigants between about 30° C. and about 100° C.

In summary, the particular temperature to which a particular dentalmaterial should be heated for enhancement without negative effectsdepends greatly upon the composition of the dental material.

FIG. 13 provides a summary of data collected to test for negativeeffects of extended periods of elevated temperature and near infrared(NIR) photon energy exposure on curing properties of dental composites.

Methods:

Three different commercially available composite brands were tested ineach of three conditions: room temperature at 20° C. (control), 80° C.in an oven, and 80° C. via photon energy. For the elevated temperaturegroup, an oven was brought to 80° C. and the composites were placedwithin for 1 hour. For NIR exposure, NIR LEDs (940 nm) were used alongwith a thermocouple and microcontroller. The LEDs were turned on at 100%with the thermocouple inserted into the composite for feedback to bringthe composite temperature up to 80° C., which took under 1 minute. Atthis point, the microcontroller switched to pulse with modulation tomaintain the constant temperature for 1 hour. Composite was dispensedand formed into a puck using a 2 mm puck mold (Paradigm Curing Discs, 3MCompany SKU: 76965) and cured for 20 seconds using a commerciallyavailable curing light. In the elevated temperature groups, dispensingwas done immediately after removing from the oven or NIR LED fixture.

Results:

As evident from the data, prolonged exposure to elevated temperaturesfrom a convection oven or by absorbed near infrared photon energy didnot statistically impact post cure microhardness values as compared toroom temperature stored dental composite. Furthermore, there was nochange in the observed aesthetics of the dental composites tested.

Conclusion:

Maintaining composite at 80° C. using photon energy did notdeleteriously impact the material.

Example 4. Absorption Measuring Experiment Using a Proximity Sensor

A test was performed using a proximity sensor (Vishay VCNL4010sensor—Fully Integrated Proximity and Ambient Light Sensor with InfraredEmitter, I²C Interface, and Interrupt Function) that incorporates bothan infrared (IR) LED at 890 nm and an IR phototransistor to measurereflected IR photon energy. Typically this sensor is used to measure thedistance of an object, however the results of our test shown in FIG. 20shows that at a fixed distance from the sensor, there is a strongcorrelation (R²=0.97) between the measured IR reflectance and theobject's change in temperature after 15 seconds of exposure to an IR LED(wavelength, power, time, and distance were all held constant betweenobjects). Objects tested were all commercially available dentalcomposite compules of different colors. Therefore, the sensor can beused to determine the amount of photon energy needed to heat a givendental material, or a material's container, to a desired temperature andoptionally maintain the desired temperature over a period of time.Additionally, the sensor's measured value can serve as a “fingerprint”to identify the inserted object to implement a closed platform system(i.e. the device would only work with a specific material or materialcontainer).

Example 5. Dental Composite Microhardness Vs Temperature

In addition to an enhancement of the flowability of the composite, theheating of the composite has been determined to result in enhancementswith respect to the hardness or durability of the composite materialwhen cured after application. To illustrate this, the followingevaluations were conducted, with the results graphically illustrated inFIG. 10.

Methods:

A custom heating setup was used to heat a 2 mm×3 mm composite puck(height×diameter) to designated temperatures (25, 40, 60, and 80° C.).Composite pucks were cured (Paradigm Curing Light, 3M, St. Paul, Minn.)at the various temperatures and kept in a dark container at 37 C for 24hours. Microhardness was measured on the sample's top and bottomsurfaces using a HMV-G Micro Hardness Tester (Shimadzu, Kyoto, Japan)under the following experimental conditions: Force setting—HV0.2(1.961N); Hold time—10 seconds. Prior to microhardness measurements, thecomposite samples were smoothened using 180, 500 and 1500 grit sandpaperto level the sample and polish the sample's surface for analysis. Fourresin based nanocomposite were tested (n=9 for each): Herculite Ultra(Kerr), Tetric EvoCeram (Ivoclar Vivadent), Filtek Supreme Ultra (3M)and Grandio (Voco). Unpaired student's t-tests (a=0.05) were used tocompare statistical significance between temperature results.

Results:

Microhardness results are summarized in the subsequent FIG. 10.Pre-heating the Grandio and Filtek composites ≥60° C. resulted instatistically significantly increased microhardness on both the top andbottom surfaces of the samples (p<0.02). Pre-heating the Tetriccomposite to 60° C. resulted in statistically significantly increasedmicrohardness on the top surface of the samples (p=0.047). Pre-heatingthe Herculite composite to 80° C. resulted in statisticallysignificantly increased microhardness on the top surface of the samples(p<0.05).

Conclusion:

Curing dental composites at elevated temperatures is favorable toincrease composite microhardness. In particular, 60° C.-80° C. is thetarget range to increase microhardness for the composites tested.Therefore, additives that act to increase the photopolymerizable dentalmaterial's temperature prior to or during curing can act as apolymerization enhancer themselves, since increased temperature leads toincreased polymerization and a higher microhardness measurement. Thus,in some aspects photon energy is used to heat dental materials,specifically dental photopolymerizable materials, to temperaturesbetween about 60° C. and about 80° C.

Example 6. Dental Composite Degree of Conversion Vs Temperature

As another measure of the enhancement of durability as a result of theheating or pre-heating of the composite prior to application and curingof the dental composite, the degree of conversion of the compositematerial at elevated temperatures was also assessed according to thefollowing evaluation, the results of which are shown in FIG. 11.

Methods:

A custom heating setup was used to heat a 2 mm×3 mm composite puck(height×diameter) to designated temperatures (25° C., 40° C., 60° C.,and 80° C.). Composite pucks were cured at the various temperatures andkept in a dark container at 37° C. for 24 hours. The DoC was measured atthe top surface of the sample by micro-attenuated total reflectancefourier transform infrared spectroscopy (micro-ATR FTIR) using a NicoletiS5 Spectrometer equipped with an iD5 ATR accessory (ThermoFisherScientific, Waltham, Mass.) at the following specifications: wave numberrange=4000-650 cm-1, 32 scans/second, and 2 cm-1 resolution. Four resinbased nanocomposite were tested (n=5 for each): Herculite Ultra (Kerr),Tetric EvoCeram (Ivoclar Vivadent), Filtek Supreme Ultra (3M) andGrandio (Voco). Unpaired student's t-tests (a=0.05) were used to comparestatistical significance between temperature results.

Results:

Degree of conversion results are shown in FIG. 11. All four compositebrands showed statistically significantly increased degree of conversion(DoC) for composites heated to 60° C. compared to 25° C. (p<0.05). Allcomposite brands, but Herculite (p=0.11), showed statisticallysignificantly increased DoC for composites heated to 80° C. compared to25° C. (p<0.03). Only Grandio showed statistically significantlyincreased DoC when heated to 40° C. compared to 25° C. (p=0.02)

Conclusion:

Curing of dental composites at elevated temperatures results in higherDoC. In particular, 60° C.-80° C. is the target range to maximize DoC.Thus, in some aspects photon energy is used to heat dental materials,specifically dental photopolymerizable materials, to temperaturesbetween about 60° C. and about 80° C.

Example 7. Polywave/Multi-Spectral Curing

As pre-heating of the photopolymerizable dental material providesenhancement to the photopolymerizable dental material upon curing, thebenefits of combined blue light at 440-500 nm and a second wavelengthabove 520 nm was evaluated. The impact of combined photon energy andcuring light emissions on composite microhardness was investigatedaccording to the following experiment, the results of which aregraphically illustrated in FIG. 12:

Methods:

A custom setup was used to investigate the simultaneous near-infraredphoton energy and curing of Filtek Supreme composite. Briefly, the setupconsisted of a 2 mm puck mold (Paradigm Curing Discs, 3M Company SKU:76965) placed above a fixed near-infrared LED die package (5 mm away; 4die 850 nm LED, LEDEngin, San Jose, Calif., operated at 1 A) and below afixed dental curing light (2 mm away; Valiant Curing Light, Vista DentalProducts, Racine, Wis.). Five different groups were tested with an n=3for each group: G1) Valiant's standard 20 s cure mode (no NIR), G2)Valiant's boost 3 s cure mode (no NIR), G3) Valiant's standard 20 scure+20 s NIR (0 s lag; i.e. simultaneous), G4) NIR (0-25seconds)+Valiant's standard 20 s cure (from 5-25 s), i.e. a 5 s NIRlead, and G5) NIR (0-13 s)+Valiant's boost 3 s cure (10-13 s), i.e. a 10s NIR lead. Composite samples were subjected to microhardness evaluationas described in example 5. Unpaired student's t-tests (a=0.05) were usedto compare statistical significance between experimental groups.

Results:

Composite hardness results are provided in the subsequent FIG. 12. G3and G4 showed statistically significantly increased microhardness on thetop side of the composite samples compared to G1 (p=0.03 and 0.02,respectively). Statistical significance was not observed comparing theresults between G2 and G5 (p=0.11); however, inter-group comparisonreveals that G5's results had higher average results for both sides ofthe sample. Thus, a larger sample set may help elucidate the true trendbetween these groups.

Conclusion:

The simultaneous or sequential use of wavelengths above 520 nm andcuring light seems to improve cured composite microhardness as thismethod does not negatively affect the curing process.

In addition, the impact of other wavelengths within the specifiedwavelength range (520 nm-2500 nm) on composite microhardness wereevaluated according to the following experimentation, the results ofwhich are graphically illustrated in FIG. 21

Methods:

A custom setup was used to investigate the simultaneous application ofphoton energy at various wavelengths and curing of Grandio SO composite.The setup consisted of a ring of 3 blue LEDs (475 nm Cree XLamp XP-E2) 5mm away from the sample with a fourth interchangeable LED in the center.The power of the blue LEDs were adjusted so that the composite samplewould be exposed to the same optical energy level as used with acommercially available curing light (Valiant Curing Light, Vista DentalProducts, Racine, Wis.). The interchangeable LEDs were adjusted so theyall emitted the same optical power output, while the optical power fromthe 3 blue LEDs was kept consistent. Optical power measurements wereperformed using an optical power meter (S310C sensor, PM100D console,Thor Labs, Newton, N.J.). Wavelengths tested by the interchangeable LEDwere 523 nm, 590 nm, 623 nm, 660 nm, 740 nm, 850 nm, and 940 nm(LedEngin LZ1). Ten seconds of exposure of the interchangeable LEDpreceded 20 seconds of combined interchangeable LED and blue LED output.In other words, the interchangeable LED emitted light for 30 seconds,while the three blue LEDs emitted light during the last 20 seconds, i.e.the photon energy within the specified wavelength leads thepolymerization light by 10 s. Composite samples were subjected tomicrohardness evaluation as described previously in “CompositeMicrohardness vs Temperature” section. Unpaired student's t-tests(a=0.05) were used to compare statistical significance betweenexperimental groups.

Results:

Microhardness data for the tested wavelengths are shown in FIG. 21. Tophardness was significantly greater using 523 nm, 590 nm, 623 nm, 660 nm,850 nm, and 940 nm. Bottom microhardness was significantly greater using523 nm, 623 nm, 660 nm, 850 nm, and 940 nm.

Conclusion:

Multiple wavelengths showed improved post-cure microhardness on the topand bottom of the puck when combined with the standard bluepolymerization light at 470 nm. These wavelengths would be advantageousto use clinically, as harder composites illustrate decreased wear inincreased longevity. Furthermore, although hydroxyapatite and waterexhibit low absorption coefficients for commercially available curinglight spectra, i.e. peak emission at 470 nm, oxyhemoglobin absorptioncoefficient is 1000-10000 times higher absorbance than the disclosedphoton energy spectra (ref FIG. 22); this is why commercially availablecuring lights pose concern for intrapulpal temperature rises and safety.Therefore, the disclosed invention can utilize photon energy between 520nm and 2500 nm to increase composite microhardness (FIG. 21), decreaseoxyhemoglobin and pulp absorbance, and improve clinical efficacy andsafety.

Furthermore, the described “lead” of the photon energy emission, priorto curing light emission, demonstrates a successful exemplary embodimentof the invention. No deleterious effects were observed by using twodiscrete emission spectra during testing, wherein one emission spectrais within the disclosed photon energy range (520 nm-2500 nm).

Example 8. Improved Heating by Incorporating a Heating Additive toDental Composite or Gutta Percha

To enhance the absorption of the dental material in the near IRwavelengths, and thus improve the conversion of applied photon energy totemperature rise of dental material, near IR dyes (i.e., a photon energyabsorption enhancer) were added. The first evaluation saw using twodifferent NIR dyes as an additive to gutta-percha and a composite andthe heating was evaluated according to the following experiment:

Methods:

Two near-infrared dyes were investigated (Nickel(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, Sigma Aldrich,Milwaukee, Wis.; and QCR # NIR848A (QCR Solutions, Port St. Lucie,Fla.). Dyes were dissolved in ˜0.3 mL chloroform (Sigma Aldrich,Milwaukee, Wis.) at varying concentrations to yield 2 w/w %, or 5 w/w %dye in gutta percha or 1 w/w %, or 2.5 w/w % dye in dental composite(Filtek Supreme). Once the dye was dissolved, powderized gutta percha ordental composite was added to the mixture and hand-blended with anadditional ˜0.5 mL chloroform until smooth. The newly formed guttapercha/composite then sat in a fume hood for −30 minutes to allow thechloroform to evaporate. Gutta percha samples were placed on a watchglass on a 120° C. hot plate for 5 minutes until soft. Gutta perchapucks were made using a custom 2 mm height×3.4 mm diameter mold. Athermistor was placed into the gutta percha pucks and the samples wereheated using an 850 nm four die LED package at a distance of 3 mm.Composite samples were formed in a similar fashion, except heat was notneeded to create the pucks.

Results:

Heating results are provided in tables 15-16 below. Table 15 shows theresults following addition of Near IR Dye #1 to Gutta-Percha. The NearIR dye #1 was Nickel(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine having anAbsorbance of 845-851 nm and an extinction coefficient of 111 L/g*cm.The test compositions included either 2% or 5% of Dye 1 in powder GuttaPercha.

TABLE 15 Near IR Ni Dye in Gutta-Percha To Tf Delta T Sample (° C.) (30s) (° C.) (° C.) 2% Dye 1 28 72 44 5% Dye 1 25 126 101 GP (no dye) Nomeasurable temperature difference

Table 16 shows the results following addition of Near IR Dye #2 toGutta-Percha. Table 17 shows the results following addition of variousconcentrations of Near IR Dye #2 to the commercially available dentalcomposite Filtek. The Near IR Dye #2 was QCR # NIR848A (Lot#0519-16A-8484) having an extinction coefficient of 330 L/g*cm. The testcompositions included either 2% or 5% Ni IR dye in powder Gutta Percha

TABLE 16 Near IR QCR Dye in Gutta-Percha To Tf (30 s) Delta T Time toGutta Percha (° C.) (° C.) (° C.) 80° C. GP + 2% Dye 2 25 96 71 24 sGP + 5% Dye 2 25 171 146  9 s

TABLE 17 Near IR QCR Dye in Filtek Dental Composite To Tf (30 s) Delta TTime to Filtek Composite (° C.) (° C.) (° C.) 80° C. Filtek without dye2 24 105 81 18 (trial 1) 22 (trial 2) Filtek + 1% Dye 2 26 178 152 7 sFiltek + 2.5% Dye 2 26 N/A N/A 9 s Filtek + 5 ppm Dye 2 24 100 76 20Filtek + 10 ppm Dye 2 23 132 109 12 (trial 1) 12 (trial 2) Filtek + 100ppm Dye 2 23 117 94 14Conclusion:

The addition of Near IR dyes significantly improves the efficiency ofthe deposited NIR photon energy to a temperature rise in the dentalmaterial and quickens the heating of dental materials, such as compositeand gutta-percha. In one embodiment, an additive is added to a dentalmaterial composition in the concentration of at least 10 ppm (0.001%)that absorbs photon energy between 520 nm-2500 nm to facilitate rapidheating of the dental material. Additionally, this additive can be addedto the dental material container.

Another test examined adding a NIR dye to composite. The heatingrate/characteristics were evaluated according to the followingexperiment, the results of which are shown graphically in FIG. 23:

Methods:

One near infrared dye was investigated (LUNIR1). The dye was weighed andplaced in a cuvette. Dental Composite (Grandio SO, VOCO GmBH) was addedin the correct amounts to create 0.1 mg of composite with a dyeconcentration of 0.10%, 0.50%, 1.0%, and 2.0% by weight. These weretested against a control of dental material only. The composite was thenexposed to a near infrared LED (940 nm LedEngin LZ1) for 15 seconds.Starting and ending temperature of the composite was measured using athermocouple placed in the composite. Unpaired student's t-tests(a=0.05) were used to compare statistical significance betweenexperimental groups.

Results:

Composite temperature change data for the tested dye concentrations areshow in FIG. 23. Statistically significant differences were foundbetween the control and each of the four dye concentrations. Nostatistical significance was found when comparing the temperaturesbetween the different dye concentration percentages. Regardless ofLUNIR1 concentration, the composite's color did not noticeably changefrom the original tooth resin shade.

Conclusion:

Adding a photon energy absorbing dye to the composite significantlyimproves the efficiency of the deposited photon energy to be convertedinto heat and a temperature rise in the dental material. There is anobserved positive trend of increased temperature rise with greater dyeconcentrations though no statistical difference. Thus, in one embodimentan additive is added to a dental material composition in theconcentration of at least 0.1% that absorbs photon energy between 520nm-2500 nm to facilitate rapid heating of the dental material.Additionally, the additive should not introduce an unnatural tooth colorchange to the dental material.

Another test examined adding a different dye to composite. Theabsorbance characteristics of the composite blend was evaluatedaccording to the following experiment, the results of which are showngraphically in FIG. 24.

Methods:

Indocyanine green (ICG) is a well-known biocompatible dye that is FDAapproved for in vivo use and has a peak absorbance at 800 nm. ICG wasdissolved in ˜0.3 mL chloroform (Sigma Aldrich, Milwaukee, Wis.) andadded at varying amounts to yield 1 ppm, 10 ppm, 100 ppm, and 1000 ppmdye in dental composite (Filtek Supreme, shade A2). The mixture was thenhand-blended until smooth and sat in a light-protected fume hood for −10minutes to allow the chloroform to evaporate (light protection wasrequired to ensure the composite wasn't cured by room light). Thesamples were then subjected to Fourier transform spectroscopy to measurethe absorbance at 800 nm.

Results:

As FIG. 24 illustrates, 10 ppm ICG resulted in a significant increase inabsorbance of the dental composite at 800 nm. Further increases in ICGconcentration resulted in increased absorbance. The absorbance of 1 ppmICG was nearly identical to 0 ppm ICG. ICG concentrations of 1 ppm and10 ppm did not noticeably change the composite color from the originalcomposite tooth shade. However, 100 ppm and 1000 ppm ICG resulted in agreen composite blend/mixture, which constitutes and unnatural toothcolor.

Conclusions:

The addition of a photon energy absorbing dye, ICG, at concentrationsgreater than 1 ppm resulted in significantly increased materialabsorption at 800 nm. 10 ppm ICG would be applicable for dentalcomposites, as the addition of 10 ppm ICG did not noticeably change thecomposite color from the original composite tooth shade. Due toaesthetic concerns, 100 ppm and 1000 ppm would not be applicable for usein dental composite. However, 100 ppm and 1000 ppm can be used innon-aesthetic procedures or in dental materials that are not concernswith aesthetics (e.g. gutta percha that is filled inside the tooth andnot cosmetically visualized).

Example 9. Far Red or Near IR Dye Additive+Composite as a Photoinitiatorto Improve Curing

A far red dye that is a combination of a photo initiator andco-initiator to dental composite and the properties of the cure wereevaluated according to the following, the results of which are shown inFIG. 26.

Methods:

Dental composite (Ivoclar Evo-Ceram) was used with a far red lightphotoinitiator (H-Nu 660, Spectra Group Limited) at varyingconcentrations from 0.005% to 0.1% by weight along with a co-initiator(Borate V) used at 1 Ox times concentration. Also tested for comparisonwere unmodified composite and composite with the co-initiator at 1% byweight without the initiator. Pucks of composite were made 2.35 mm deepand 3.45 mm wide. Curing was performed on all variables with a far red(660 nm LedEngin LZ1) and blue (475 nm Cree XLamp XP-E2) LEDcombination. The red LED was first activated for 10 seconds, followed by20 seconds of simultaneous red and blue LED activation. Also tested as acontrol was an additional blue LED in place of the red on the unmodifiedcomposite and composite only with the coinitiator. Surface microhardnesswas measured on the top and bottom of the composite puck after curing.Unpaired student's t-tests (a=0.05) were used to compare statisticalsignificance between experimental groups.

Results:

Microhardness data for the tested conditions are shown in FIG. 26. Asignificant increase was found on the top for 0.005% 660 nminitiator+0.05% Borate V. Significantly lower hardness was found for0.1% 660 nm initiator+1.0% Borate V, 0.05% 660 nm initiator+0.5% BorateV, and 0% 660 nm initiator+1.0% Borate V. Additionally, a visible colorchange from green/blue to standard A2 shade was visualized afterphotopolymerization for the various compositions, as shown in FIG. 27.In particular, the green/blue color was unnoticeable post-cure for660HNu concentrations equal to or below 0.05%. Thus, theseconcentrations can be used to provide a visible indication of acomplete/successful cure to the clinician. Conversely, remnantgreen/blue color is observed in the 0.1%660HNu samples post-cure.

Conclusion:

Using an additional initiator and coinitiator along with a far redwavelength has an effect on the microhardness of cured composite. At toohigh of a concentration, it can actually have an adverse effect on thehardness of the bottom side, potentially because energy is absorbed bythe initiators before it can reach this depth. However, a concentrationcan be selected that will improve the microhardness compared to usingblue light alone. In particular, the addition of 0.005% 660H-Nu and0.05% BorateV to commercially available dental composites, andsubsequent curing using 660 nm and blue (e.g. 470 nm) light would resultin a harder composite post-cure.

Example 10. Far Red or Near Infrared Dye Additive+Housing Material

To enhance the absorption of the dental material housing in the far redor near IR wavelengths, and thus improve the conversion of appliedphoton energy to temperature rise of dental material, a plastic with aNIR dye was evaluated according to the following; the results of whichare shown graphically in FIG. 25.

Methods:

An NIR LED (940 nm LZ1 LedEngin powered at 1 A) was used to heat variousplastic materials of similar thickness. A thermocouple was adhered tothe plastic on the side opposite exposure to the LED emission, centeredover the LED. The LED was activated for 30 seconds, and an additional 30seconds of temperature data were recorded after the LED was turned off.Materials tested were poly(methyl methacrylate) (PMMA) (clear, orange,black and white colored), polycarbonate (PC) embedded with NIR absorbingdye (resulting plastic was clear orange in appearance), and twocommercialized composite compules (black and blue colored).

Results:

Heating curves for the materials are shown in FIG. 25. Both the rate ofchange and peak temperature change are greater for the PC with the NIRdye. Of the other materials, the black composite compule was the nextbest for heating, but the peak temperature was 60% lower than that ofthe PC with NIR dye.

Conclusion:

Adding an NIR dye to plastic material improves the efficiency of thedeposited NIR photon energy to be converted into a temperature rise.

Example 11. Devices for the Heating of Dental Material Compositions andApplication of Dental Material Compositions, and Devices for the Heatingof Dental Material Compositions and Curing of Dental PhotopolymerizableCompositions

Described herein are example embodied devices for performing theapplication of the dental material, for example dental composite. Oneexemplary embodiment of a dispensing or delivery device is illustratedin FIGS. 14-15. The device has a body including a handle and an actuatoror trigger that operates to dispense the composite form the device. Theactuator can additionally be formed as a spring-biased grip as shown inFIG. 16. As shown in FIG. 15, the body can also include a light-emitterthat emits near IR light/photon energy and a compule is furtherreleasably attached to the body adjacent to the emitter such that lightfrom the emitter strikes the compule and/or a dental material containedtherein. The light/photons from the emitter strike the compule and/ordental material and affect the dental material by heating the materialto the desired temperature and subsequently the trigger is operated todispense the dental material from the compule. When exhausted, thecompule can be disengaged from the body and a new compule attachedthereto to heat and dispense additional dental material using thedevice. The body can further include an internal power source (notshown) such as a battery, such that the device is cordless.Alternatively, the device can be connected to a suitable exterior powersource (not shown) such as via a plug (not shown) operably connected tothe device and releasably engageable with the power source.

The device may further include or be formed as a curing light source(not shown) that can be operated consecutively or simultaneously withthe near IR emitter, where the IR emitter can be a part of the curingdevice. The device also includes suitable actuators or buttons for theactivation of the emitter and/or light source. In addition, the devicemay include or be formed as a curing light source (not shown) that canbe operated consecutively or simultaneously with the near IR emitter,where the IR emitter can be a part of the curing device.

Referring to FIG. 28, one exemplary embodiment of a dispensing ordelivery device is illustrated. The device 1 has a main outer bodyincluding an outer side housing 2, a hand held grip 3 for holding thedevice, a base 4, an actuator 5, a top housing 6, and a removableautoclavable sleeve 7 overlaying a removable compule 8 that is capableof containing a dental material described herein. The grip 3 furtherincludes a removable rechargeable energy source door 9 having a holdingclip 11. The top housing 6 further overlays one or more LED indicators12 and the device further contains an on/off button or switch 13.

Referring to FIG. 29, which shows another side perspective of device 1described above and a distal tip portion 14 of the device. As shown thedistal tip portion 14 contains a compule 8 that is overlayed byautoclavable sleeve 7. Compule 8 is attached distal to a plunger 16,which extends into compule 8 after depressing actuator 5 releasing adental material from orifice 15.

Referring now to FIGS. 30 and 31 are side sagittal perspectives ofdevice 1 with outer side housing 2 and autoclavable sleeve 7 removed. Asshown, the device contains a main printed circuit board (PCB) 24 that isin connection with rechargeable energy source 25. PCB 24 is furtherconnected to a wire or wire ribbon 23 that is connected to a secondaryPCB 18 having one or more control sensors 20 and one or more photonenergy emitters 21 mounted thereto. Overlaying the photon energyemitters 21 is a lens 17, such that the photon energy emitters 21 are inclose proximity (e.g., less than 1 cm) to compule 8. As describedherein, the one or more photon energy emitters 21 emit photon energythat is absorbed by one or more components of a dental materialcontained in compule 8 causing it to heat. Additionally, as describedherein, the one or more photon energy emitters 21 emit photon energythat is absorbed by one or more components of a dental materialcontainer, such as a compule 8, causing the dental material container toheat and thereby heat the dental material contained therein. SecondaryPCB 18 may also function as a primary heat sink for the one or morephoton energy emitters 21 mounted thereto. In addition, overlayingsecondary PCB 18 is a secondary heat sink 19, which may comprise aportion of the overlaying device top housing 6 or nose cone bottom 18.FIG. 30 bottom image shows a side sagittal perspective of distal tipportion 14 of the device as described above.

Referring now to FIG. 32 is shown an expanded version of the device. Asshown is an outer side housing 2L (left side housing) and 2R (right sidehousing), top housing 6, a nose cone bottom 22, a hand held grip 3 forholding the device, base 4, a rechargeable energy source door 9 having aholding clip 11 on the right and left side, an actuator 5, removableautoclavable sleeve 7, and LED indicators 12. Also shown is plunger 16hingedly connected to actuator 5 extending distally to compule 8.Further shown is main PCB 24 having at least one photon energy emissionemitter source 21 connected to a rechargeable energy source 25 via aconnected wire or wire ribbon 23. Secondary PCB 18 is shown havingmultiple photon energy emitters 21 mounted thereto and disconnected fromwire or wire ribbon 23. Lens 17 that overlays the one or more photonemitters 21 is shown in close proximity (e.g., less than 1 cm) tocompule 8.

FIGS. 17-19 and 35 are embodiments of packages of photon emitters (i.e.LEDs) that can be incorporated for the disclosed multispectral devicedescribed herein that emits at least two discrete emission spectra forcuring the dental composite and for the application of photon energy forheating. In one aspect, the LEDs can reside on two separate PCBs and beeither on the same plane or a different plane. Although not shown inthese figures, the 2 different emission sources can be placed on thesame PCB and reside on the same plane, or lastly a single LED packagecan be created that incorporated multiple die(s) for the emission ofdifferent spectra. In one aspect, the various photon energy sources(i.e. LEDs) are on separate PCBs on separate planes as illustrated inFIGS. 17-19 and 35 as this configuration allows for improved collimationand illumination of the light/photon energy compared to multiple dies onthe same LED package. Specifically, in one aspect, a configurationentails three LEDs oriented in a clover configuration (i.e. spaced 120°apart) on a PCB that is located in an elevated position relative toanother PCB containing one LED (see FIGS. 17 and 35). This configurationallows for closer spacing of the LEDs for easier collimation of theLEDs' spectral radiation patterns using smaller sized optical components(e.g. reflector, collimator, etc) and an even illumination field.

Further detailing the embodied LED configurations and referring to FIGS.17-19, the light or photon emission portion of the multispectral device38 can include different sets of photon emitters 21 a which can beplaced on the same printed circuit board (PCB) and reside on the sameplane, or they can reside on two separate PCB and be either on the sameplane or a different plane, or lastly a single LED package can becreated that incorporated multiple die(s) for the emission of differentwavelengths of light or photons of different energies.

In FIG. 17, the multispectral device 38 further includes a collimatorbody or device housing 30 for the emitter(s) 21 a that enclose LEDs 32a, 32 b, and 32 c, where the LEDs 32 a, 32 b, and 32 c are mounted onthe same or different PCB 27 a and 27 b that can be disposed indifferent planes. LEDs 32 a, 32 b, and 32 c must emit at least twodistinct emission spectra, wherein at least one emission spectra iswithin the specified photon energy range. The LEDs 32 a, 32 b, and 32 care disposed within the collimator body or device housing 30 inalignment with a collimator surface 29 a to direct the light and/orphotons out of the collimator body or device housing 30 where desiredthrough a lens 29 b. In FIGS. 17 and 18 the LEDs 32 a are located aroundthe exterior of the collimator body or device housing 30, with the LED32 c disposed within collimator body or device housing 30 as illustratedin the embodiment of FIG. 17.

Another embodied device is shown in FIGS. 33 and 34, which is amultispectral device 38 for curing and/or heating a dental material.Device 38 includes a central photon energy emitter (i.e. an LED) 35 withthree radially placed photon energy emitters (i.e. LEDs) 34. The centralphoton energy emitter 35 is placed on a primary heat sink that iscoupled to the thermally conductive main body 41. The three radiallyplaced photon energy emitters 34 are placed on a separate primary heatsink that is parallel to the central photon energy emitter's 35 primaryheat sink and is also coupled to the thermally conductive main body 41.Device 38 may optionally include an optical transilluminator 39. Device38 includes a PCB 43, button 42, detachable and rechargeable batterypack 44, and rotation knob 40 for selecting a mode of operation.

Referring now to FIG. 35 is shown a setup 33 for inclusion within themultispectral device 38. The setup 33 contains 3 radially positionedphoton energy emitters (i.e. LEDs) 34 on heat sink/PCB 36, aroundcentral LED 35 that is attached to separate heat sink/PCB 37 which isparallel to the other heat sink/PCB 36. Both heat sinks are coupled tothe thermally conductive main body 41. In this example, the four LEDs 34and 35 emit at least two distinctly different spectra; at least onespectra is used to elevate the photopolymerizable material above ambienttemperature and at least one spectra is used to cure thephotopolymerizable material.

The following statements are illustrative and within the scope of theembodiments of the invention described herein.

Statement 1. A method of treating a tooth of a subject in need thereofcomprising:

heating a dental photopolymerizable material above ambient temperaturewith a device having a photon energy emission source that emits a photonenergy that:

-   -   does not photopolymerize the material,    -   is absorbed by the dental photopolymerizable material, a dental        photopolymerizable material container, or a heating additive,        and    -   increases one or more properties comprising:        -   energy conversion efficiency from photon energy to heat or,        -   heating rate of the dental photopolymerizable material; and

applying the heated dental photopolymerizable material to a toothsurface cavity.

Statement 2. The method according to statement 1, wherein the photonenergy increases the heating rate of a dental photopolymerizablematerial compared to heating the dental photopolymerizable materialwithout photon energy.

Statement 3. The method according to any one of statements 1-2, whereinthe device emits a photon energy of about 0.49 eV-2.38 eV (2500 nm-520nm).

Statement 4. The method according to any one of statements 1-3, whereinthe device emits a photon energy of about 1.23 eV-2.06 eV (1000 nm-600nm).

Statement 5. The method according to any one of statements 1-4, whereinthe dental photopolymerizable material is heated to a temperature ofabout 50° C. to about 250° C.

Statement 6. The method according to any one of statements 1-5, whereinthe dental photopolymerizable material is heated to a temperature ofabout 60° C. to about 80° C.

Statement 7. The method according to any one of statements 1-6, furthercomprising curing the dental photopolymerizable material.

Statement 8. The method according to any one of statements 1-7, whereinthe dental photopolymerizable material comprises composite resins,highly filled composite resins, glass ionomer resins, sealants, cements,cavity liners, or combinations thereof.

Statement 9. The method according to any one of statements 1-8, furthercomprising curing the dental photopolymerizable material by applying asecond source of photon energy that emits a wavelength suitable forabsorption by the photopolymerizable material to initiatepolymerization.Statement 10. The method according to any one of statements 1-9, whereinan applied photon energy for heating the dental photopolymerizablematerial does not overlap with an absorbance of a photoinitiator presentin the dental photopolymerizable material.Statement 11. The method according to any one of statements 1-10,wherein the dental photopolymerizable material or the dentalphotopolymerizable material container further comprises a heatingadditive, a thermal conductivity enhancer, or a polymerization enhancer,or combinations of the same.Statement 12. The method according to any one of statements 1-11,wherein the heating additive is a dye having an absorption spectra thatoverlaps with an emission spectra of the photon energy emitted from thephoton energy source.Statement 13. The method according to any one of statements 11-12,wherein the thermal conductivity enhancer is an additive that improvesthe thermal conductivity of the dental photopolymerizable material orthe dental photopolymerizable material container.Statement 14. The method according to any one of statements 11-13,wherein the thermal conductivity enhancer is selected from graphitefibers, graphene flakes, ceramic particles, metal oxides, metalparticles, carbon nanotubes, and combinations of the same.Statement 15. The method according to any one of statements 1-14,wherein the photon energy that is at an absorption wavelength of thedental photopolymerizable material or a dental photopolymerizablematerial container is emitted during a curing step or just prior to acuring step of the dental photopolymerizable material.Statement 16. The method according to any one of statements 1-15,wherein the application of the photon energy that is at an absorptionwavelength of the dental photopolymerizable material or a dentalphotopolymerizable material container increases one or more post-cureproperties of the dental photopolymerizable material, selected fromdegree-of-conversion and hardness, compared to a dentalphotopolymerizable material that has not been heated with the photonenergy that is at an absorption wavelength of the dentalphotopolymerizable material or a dental photopolymerizable materialcontainer.Statement 17. The method according to any one of statements 1-16,wherein the application of the photon energy that is at an absorptionwavelength of the dental photopolymerizable material or a dentalphotopolymerizable material container stimulates one or morephotochemical effects selected from: photodegradation, photobleaching,or photocatalysis of the dental photopolymerizable material.Statement 18. A photopolymerizable dental composition comprising:

unreacted monomer(s),

filler(s),

at least one photoinitiator, and

a heating additive that increases one or more properties comprising: theenergy conversion efficiency from photon energy to heat or increasing aheating rate of the dental photopolymerizable material, wherein theheating additive does not impart an unnatural tooth color to thephotopolymerizable dental composition after photopolymerization.

Statement 19. The composition of statement 18, wherein the heatingadditive and the at least one photoinitiator are activated by distinctlydifferent photon energy spectra.

Statement 20. The composition according to any one of statements 18-19,wherein the heating additive comprises one or more of the followingproperties: a high absorbance between 0.49 eV-2.38 eV (2500 nm-520 nm),compatible with a dental photopolymerizable material, stable attemperatures greater than room temperature, soluble and dispersiblewithin the dental photopolymerizable material, does not negativelyaffect a dental photopolymerizable material performance, or has a highconversion efficiency from photon energy to heat or a combination ofproperties thereof.Statement 21. The composition according to any one of statements 18-20,wherein the heating additive comprises a photon energy absorptionenhancer or a thermal conductivity enhancer or a combination thereof.Statement 22. The composition according to statement 21, wherein thephoton energy absorption enhancer is present in the dentalphotopolymerizable material at a concentration of up to about 10% byweight of the dental photopolymerizable material.Statement 23. The composition according to any one of statements 21-22,wherein the photon energy absorption enhancer is present in the dentalphotopolymerizable material at a concentration of about 0.001% to about0.5%.Statement 24. The composition according to any one of statements 21-23,wherein an area-intersection of a normalized absorbance spectra of thephoton energy absorption enhancer and a normalized emission spectra of aphoton energy source is at least 10% of an area-under-the-curve foreither spectra.Statement 25. The composition according to statement 24, wherein thearea-intersection of the normalized absorbance spectra of the photonenergy absorption enhancer and a normalized emission spectra of thephoton energy source is at least 25% of an area-under-the-curve foreither spectra.Statement 26. The composition according to any one of statements 24-25,wherein the area-intersection of the normalized absorbance spectra ofthe photon energy absorption enhancer and a normalized emission spectraof the photon energy source is at least 50% of an area-under-the-curvefor either spectra.Statement 27. The composition according to any one of statements 21-26,wherein the thermal conductivity enhancer is an additive that improvesthe thermal conductivity of the dental photopolymerizable material.Statement 28. The composition according to any one of statements 21-27,wherein the thermal conductivity enhancer is selected from: graphiteparticles, graphene particles, ceramic particles, metal oxide particles,metal particles, carbon nanotubes, and combinations thereof.Statement 29. The composition according to any one of statements 21-28,wherein the thermal conductivity enhancer is present in the dentalphotopolymerizable material at a concentration of about of 0.01% toabout 90% by weight of the dental photopolymerizable material.Statement 30. The composition according to any one of statements 21-29,wherein the thermal conductivity enhancer is present in the dentalphotopolymerizable material at a concentration of about of 1% to about10% by weight of the dental photopolymerizable material.Statement 31. The composition according to any one of statements 18-30,wherein the composition further comprises a polymerization enhancerconsisting of a photoinitiator or a co-initiator or a combinationthereof.Statement 32. The composition of statement 31, wherein thepolymerization enhancer increases a photopolymerization of aphotopolymerizable monomer present in the dental photopolymerizablematerial.Statement 33. The composition according to any one of statements 31-32,wherein the polymerization enhancer increases one or more propertiesconsisting of:

improving polymerization, improving depth-of-cure, improvingdegree-of-conversion using photon energy, and combinations of propertiesthereof.

Statement 34. The composition according to any one of statements 18-33,wherein the heating additive comprises a dye, which exhibits anabsorbance between 0.49 eV-2.38 eV (2500 nm-520 nm).

Statement 35. The composition of statement 18-34, wherein the dyecomprises about 0.001% to about 10% by weight of the composition.

Statement 36. The composition according to any one of statements 18-35,wherein the composition comprises:

-   -   a. an unreacted acrylate monomer comprising about 5-30% by        weight;    -   b. an inorganic filler comprising about 60-95% by weight;    -   c. a photoinitiator comprising about 0.001-0.5% by weight;    -   d. a co-initiator comprising about 0.001-1% by weight; and    -   e. a dye, which exhibits an absorbance between 0.49 eV-2.38 eV        (2500 nm-520 nm) comprising about 0.001-10% by weight.        Statement 37. The composition according to any one of statements        18-36, wherein the composition comprises:    -   a. an unreacted acrylate monomer comprising 40-90% by weight;    -   b. an inorganic filler comprising 1-20% by weight;    -   c. a photoinitiator comprising 0.001-0.5% by weight;    -   d. a co-initiator comprising 0.001-0.5% by weight; and    -   e. a dye, which exhibits an absorbance between 0.49 eV-2.38 eV        (2500 nm-520 nm) comprising 0.001-10% by weight.        Statement 38. A method of treating a tooth of a subject in need        thereof comprising heating the composition of any one of        statements 18-37 with a device having a photon energy emission        source that emits a photon energy that is at an absorption        wavelength of the composition or a heating additive present in        the composition and applying the heated composition to a surface        of the tooth.        Statement 39. A dental composition, comprising polyisoprene,        inorganic filler(s), radiopacifier, wax(es) or resin(s), and a        heating additive that increases one or more properties        comprising: energy conversion efficiency from photon energy to        heat or increasing a heating rate of the dental composition.        Statement 40. The composition of statement 39, wherein the        polyisoprene comprises natural or synthetic gutta percha.        Statement 41. The composition according to any one of statements        39-40, wherein the polyisoprene comprises about 10% to about 30%        by weight of the composition.        Statement 42. The composition according to any one of statements        39-41, wherein the filler comprises about 50% to about 85% by        weight of the composition.        Statement 43. The composition according to any one of statements        39-42, wherein the radiopacifier comprises about 1% to about 35%        by weight of the composition.        Statement 44. The composition according to any one of statements        39-43, wherein the wax(es) or resin(s) comprise about 1% to        about 10% by weight of the composition.        Statement 45. The composition according to any one of statements        39-44, wherein the heating additive comprises about 0.001% to        about 10% by weight of the composition.        Statement 46. The composition of according to any one of        statements 39-45, wherein the composition comprises:    -   a. natural gutta percha or synthetic gutta percha comprising        about 10-30% by weight of the composition;    -   b. an inorganic filler comprising about 50-85% by weight of the        composition;    -   c. a radiopacifier comprising about 1-35% by weight of the        composition;    -   d. a wax or resin comprising about 0-10% by weight of the        composition; and    -   e. a heating additive, which exhibits an absorbance between 0.49        eV-2.38 eV (2500 nm-520 nm) comprising about 0.001-10% by weight        of the composition.        Statement 47. A method of treating a tooth of a subject in need        thereof comprising heating the composition of any one of        statements 39-46 with a device having a photon energy emission        source that emits a photon energy that is at an absorption        wavelength of the composition or a heating additive present in        the composition and applying the heated composition to a surface        of the tooth.        Statement 48. A photopolymerizable dental composition        comprising:

unreacted monomer(s),

filler(s),

at least two photoinitiators, wherein at least one of the twophotoinitiators is activated by photon energy within a range of 0.49eV-1.90 eV (2500 nm-650 nm), and at least one of the otherphotoinitiator(s) is activated by photon energy outside this photonenergy range,

at least one co-initiator, wherein the at least one co-initiatorconsists of a borate derivative; and

wherein the photoinitiators do not impart an unnatural tooth color tothe photopolymerizable dental composition after photopolymerization.

Statement 49. The composition of statement 48, wherein the twophotoinitiators comprise a type I or a type II photoinitiator or acombination thereof.

Statement 50. The composition of any one of statements 48-49, whereinthe photopolymerizable material comprises two type II photoinitiators.

Statement 51. The composition according to any one of statements 48-50,wherein the photoinitiator that is activated by photon energy within therange of 0.49 eV-1.90 eV (2500 nm-650 nm) enhances photopolymerization.

Statement 52. The composition according to any one of statements 48-51,wherein the photoinitiator that is activated by photon energy within therange of 0.49 eV-1.90 eV (2500 nm-650 nm) is present at a concentrationof about 0.0001% to about 0.5% by weight of the composition.Statement 53. The composition according to any one of statements 48-52,wherein the photoinitiator that is activated by photon energy within therange of 0.49 eV-1.90 eV (2500 nm-650 nm) is present at a concentrationof about 0.001% to about 0.1% by weight of the composition.Statement 54. The composition according to any one of statements 48-53,wherein the borate derivative is borate V.Statement 55. The composition according to any one of statements 48-54,wherein the borate derivative is at least 10 times more concentratedthan the at least one photoinitiator that is activated by photon energywithin the range of 0.49 eV-1.90 eV (2500 nm-650 nm).Statement 56. The composition according to any one of statements 48-55,wherein the photoinitiator that is activated by photon energy within therange of 0.49 eV-1.90 eV (2500 nm-650 nm) is photobleached and/or isconsumed during a photopolymerization process occurring at 0.49 eV-1.90eV (2500 nm-650 nm) to reduce its visible color.Statement 57. The composition according to any one of statements 48-56,wherein the photoinitiator that is activated by photon energy within therange of 0.49 eV-1.90 eV (2500 nm-650 nm) promotes material curing byincreasing radical formation and simultaneously bleaches as formedradicals deplete providing a visible change to indicate complete curing.Statement 58. The composition according to any one of statements 48-57,wherein the composition comprises:

-   -   a. an unreacted acrylate monomer comprising about 5-30% by        weight;    -   b. an inorganic filler comprising about 60-95% by weight;    -   c. a first photoinitiator comprising about 0.001-0.5% by weight;    -   d. a second photoinitiator, which exhibits an absorbance between        0.49 eV-1.90 eV (2500 nm-650 nm), comprising about 0.001-0.5% by        weight; and    -   e. a borate derivative co-initiator comprising about 0.01-5% by        weight.        Statement 59. The composition according to any one of statements        48-58, wherein the composition comprises:    -   a. an unreacted acrylate monomer comprising 40-90% by weight;    -   b. an inorganic filler comprising 1-20% by weight;    -   c. a first photoinitiator comprising 0.001-0.5% by weight;    -   d. a second photoinitiator, which exhibits an absorbance between        0.49 eV-1.90 eV (2500 nm-650 nm), comprising 0.001-0.5% by        weight; and    -   e. a borate derivative co-initiator comprising 0.01-5% by        weight.        Statement 60. A method of treating a tooth of a subject in need        thereof comprising heating the composition of any one of        statements 48-59 with a device having a photon energy emission        source that emits a photon energy that is at an absorption        wavelength of the composition or a photoinitiator present in the        composition and applying the heated composition to a surface of        the tooth.        Statement 61. A material container comprising a thermoplastic        resin and at least one photon energy absorption enhancer        additive forming the container that increases one or more        properties comprising:

increasing energy conversion efficiency from photon energy to heat, or

increasing a heating rate of the material contained within,

wherein the at least one photon energy absorption enhancer additive hasan optical density value greater than 1 for photon energy between 0.49eV-2.38 eV (2500 nm-520 nm) after thermoplastic injection molding.

Statement 62. The container of statement 61, wherein the containerfurther comprises a pigment, a colorant, a plasticizer, or a filler, ora combination thereof.

Statement 63. The container according to any one of statements 61-62,wherein the container comprises an additional photon energy absorptionenhancer additive, or at least one thermal conductivity enhancer, orcombinations thereof as an integral part of the container.Statement 64. The container according to statement 63, wherein thephoton energy absorption enhancer additive is present in the containerat a concentration of about 0.01% to about 20% by weight of a dentalphotopolymerizable material container.Statement 65. The container according to any one of statements 63-64,wherein the photon energy absorption enhancer additive is present in thecontainer at a concentration of about of 0.1% to about 5% by weight of adental photopolymerizable material container.Statement 66. The container according to any one of statements 61-65,wherein an area-intersection of a normalized absorbance spectra of thephoton energy absorption enhancer additive and a normalized emissionspectra of a photon energy source is at least 10% of anarea-under-the-curve for either spectra.Statement 67. The container according to statement 66, wherein thearea-intersection of the normalized absorbance spectra of the photonenergy absorption enhancer additive and a normalized emission spectra ofthe photon energy source is at least 25% of an area-under-the-curve foreither spectra.Statement 68. The container according to any one of statements 66-67,wherein the area-intersection of the normalized absorbance spectra ofthe photon energy absorption enhancer additive and a normalized emissionspectra of the photon energy source is at least 50% of anarea-under-the-curve for either spectra.Statement 69. The container according to any one of statements 63-68,wherein the thermal conductivity enhancer is an additive that improvesthe thermal conductivity of the dental material container.Statement 70. The container according to any one of statements 63-69,wherein the thermal conductivity enhancer is selected from: graphiteparticles, graphene particles, ceramic particles, metal oxide particles,metal particles, carbon nanotubes, and combinations thereof.Statement 71. The container according to any one of statements 63-70,wherein the thermal conductivity enhancer is present in the housing at aconcentration of about 0.1% to about 50% by weight.Statement 72. The composition according to any one of statements 63-71,wherein the thermal conductivity enhancer is present in a dentalphotopolymerizable material container at a concentration of about 1% toabout 10% by weight of the dental photopolymerizable material container.Statement 73. The container according to any one of statements 61-72,wherein the housing sufficiently blocks light from transmitting throughthe container to a dental photopolymerizable material housed therein,thereby preventing the dental photopolymerizable material from beingcured within the container.Statement 74. The container according to any one of statements 61-73,wherein the thermoplastic resin comprises about 50% to about 95% byweight of the container.Statement 75. The container according to any one of statements 61-74,wherein the photon energy absorption enhancer additive comprises about0.1% to about 50% by weight of the composition.Statement 76. The container according to any one of statements 61-75,wherein the container comprises the thermoplastic resin comprising about95% by weight of the container and the heating additive comprising about5% by weight of the container.Statement 77. A method of treating a tooth of a subject in need thereofcomprising heating the container of any one of statements 61-76, whereinthe container comprises a dental material, wherein the container isheated with a device having a photon energy emission source that emitsphoton energy that is at an absorption wavelength of the container or aheating additive present in the container, or the dental material housedin the container and applying the heated dental material to a surface ofthe tooth.Statement 78. A container for holding a dental material according to anyone of statements 61-77 made by a process comprising:

-   -   a). heating a thermoplastic resin to at least its softening        point;    -   b). maintaining and controlling the resin temperature to at        least its softening point;    -   c). adding an additive at about 0.1-5%, that has a high photon        energy absorbance between 520 nm-2500 nm, and optionally a        dispersant while maintaining and controlling the resin        temperature to at least it softening point;    -   d). mixing the mixture of a-c while maintaining temperature to        at least the resin's softening point to homogenize the mixture;        and    -   e). extruding the heated mixture of a-d into a mold cavity        comprising the dental material container shape and allowing it        to cool prior to removal from the cavity.        Statement 79. A container for holding a dental material        according to any one of statements 61-77 made by a process        comprising:    -   a). heating a thermoplastic resin to at least its softening        point;    -   b). maintaining and controlling the resin temperature to at        least its softening point;    -   c). adding an additive at about 0.1-5%, that has a high photon        energy absorbance between 520 nm-2500 nm, and optionally a        dispersant while maintaining and controlling the resin        temperature to at least it softening point;    -   d). mixing the mixture of a-c while maintaining temperature to        at least the resin's softening point to homogenize the mixture;        and    -   e). making pellets from the mixture of a-d that can be later        used for injection molding a dental material container.        Statement 80. The container according to any one of statements        61-79, wherein the made container is filled with a dental        material.        Statement 81. A device for heating a dental material and        applying the heated dental material to a tooth surface or cavity        comprising:    -   a. a body;    -   b. a plunger mounted movably within the body for engaging with a        dental material container;    -   c. an actuation means connected to the plunger to controllably        dispense the dental material from the dental material container;    -   d. a distally mounted photon energy emission source, wherein the        photon energy emission source consists of a electroluminescence        source that produces between 0.5 watts and 20 watts of optical        power;    -   e. a rechargeable power source, wherein the electroluminescence        source is in electrical communication with the rechargeable        power source;    -   f. a primary heat sink located within the device body or        constitutes a part of the device body, wherein the        electroluminescence source is coupled to the primary heat sink        located; and    -   g. a receptacle on the device body for securably receiving the        dental material container, such that the dental material        container is held within close proximity to the        electroluminescence source.        Statement 82. The device according to statement 81, wherein the        photon energy source is capable of emitting photon energy        between 0.49 eV-2.38 eV (i.e. 2500 nm-520 nm).        Statement 83. The device according to any one of statements        81-82, wherein the photon energy emission source emits photon        energy between 1.24 eV-1.77 eV (i.e. 1000 nm-700 nm).        Statement 84. The device according to any one of statements        81-83, wherein the electroluminescence source comprises a light        emitting diode (LED) or a laser diode or a combination thereof.        Statement 85. The device according to any one of statements        81-84, wherein the electroluminescence source is less than about        1 cm from a dental material container having a dental material        therein.        Statement 86. The device according to any one of statements        81-85, wherein the device further comprises a collimator        comprising a lens or fiber optic for increasing the photon        energy irradiance to the container having the dental material.        Statement 87. The device according to any one of statements        81-86, wherein the primary heat sink is coupled to a secondary        heat sink contained within the device, or that comprises part of        the housing of the device, wherein the secondary heat sink        prevents the device from reaching an unsafe elevated temperature        above 50° C.        Statement 88. The device according to any one of statements        81-87, wherein the primary heat sink or secondary heat sink is        coupled to a heat pipe, wherein the heat pipe prevents the        device from reaching an elevated temperature.        Statement 89. The device according to any one of statements        81-88, further comprising a heat sensor, wherein the heat sensor        prevents the device from reaching an elevated temperature, which        may degrade the dental material or may pose a danger to an        operator or a patient being treated with the device; wherein the        heat sensor is indirectly capable of monitoring the temperature        of the dental material and reducing or removing power output of        the photon energy source.        Statement 90. The device according to any one of statements        81-89, further comprising a loop control feedback system for        maintaining a desired temperature without reaching undesirable        temperatures, which may degrade the dental material or may pose        a danger to an operator or a patient being treated with the        device.        Statement 91. The device according to any one of statements        81-90, further comprising an absorption sensor for determining        the absorption characteristics of a dental material or dental        material container, wherein the sensor provides an output for        adjusting power and/or duration of the photon energy source for        achieving a desired temperature of the dental material.        Statement 92. The device according to any one of statements        81-91, further comprising an additional light source for curing        dental photopolymerizable materials.        Statement 93. The device according to any one of statements        81-92, wherein the additional light source emits a light at a        wavelength of about 365 nm-500 nm.        Statement 94. The device according to any one of statements        81-93, wherein the additional light source for curing dental        photopolymerizable materials emits between 500 mW and 3 W of        optical power.        Statement 95. The device according to any one of statements        81-94, wherein the additional light source for curing dental        photopolymerizable materials a emits between 700 mW and 1.5 W of        optical power.        Statement 96. The device according to any one of statements        81-95, wherein the photon energy emission output leads, lags, or        is simultaneously used with the photon energy emission output of        the additional light source for curing dental photopolymerizable        materials.        Statement 97. The device according to any one of statements        81-96, wherein the curing light and photon energy sources are        arranged distally on the device for access to an oral cavity of        a patient.        Statement 98. A handheld multispectral device for enhancing the        cure of photopolymerizable dental materials, the device        comprising:    -   a. a thermally conductive body;    -   b. at least four discrete distally mounted photon energy        emission source(s) that produce at least two discrete emission        spectra, wherein;        -   a. one photon energy source is centrally located, and at            least three photon energy sources are located radially about            the centrally located photon energy source;        -   b. the output of the centrally located photon energy            emission source leads, lags, or is simultaneously used with            the output of the at least three radially located photon            energy emission sources;        -   c. at least one emission spectra is used for curing the            photopolymerizable dental material, and at least one            emission spectra is used to elevate the photopolymerizable            dental material's temperature above ambient temperature            during curing;        -   d. the at least four photon energy emission sources consists            of light emitting diodes;    -   c. the at least four discrete photon energy emission sources are        coupled to at least one primary heat sink located within the        device body;    -   d. the at least one primary heat sink is coupled to the        thermally conductive body; and    -   e. the light emitting diodes are in electrical communication to        a direct current power source.        Statement 99. The device according to statement 98, wherein the        direct current power source comprises a detachable, rechargeable        power source.        Statement 100. The device according to any one of statements        98-99, wherein at least three radially mounted LEDs are arranged        on a primary heat sink around the centrally located LED, which        is on a separate primary heat sink, to provide a near uniform        beam profile and illumination field.        Statement 101. The device according to any one of statements        98-100, wherein the at least four LEDs are collimated to produce        about a 1 cm spot size at a distance between 1-10 mm.        Statement 102. The device according to any one of statements        98-101, wherein the at least one photon energy emission source        for curing the photopolymerizable dental material emits light        between 365 nm-500 nm at an optical power of between 500 mW and        3 W.        Statement 103. The device according to any one of statements        98-102, wherein the at least one photon energy emission source        for elevating the photopolymerizable dental material's        temperature above ambient temperature during curing emits light        between 520 nm-2500 nm at a power between 500 mW and 3 W of        optical power. 104. A method of treating a tooth of a subject in        need thereof comprising heating a dental composite material or a        container comprising the dental composite material with the        device according to any one of any one of statements 81-103.

Although the invention herein has been described in connection withdescribed embodiments thereof, it will be appreciated by those skilledin the art that additions, modifications, substitutions, and deletionsnot specifically described may be made without departing from the spiritand scope of the invention as defined in the appended claims. It istherefore intended that the foregoing detailed description be regardedas illustrative rather than limiting, and that it be understood that itis the following claims, including all equivalents, that are intended todefine the spirit and scope of this invention.

What is claimed is:
 1. A material container comprising a thermoplasticresin and at least one photon energy absorption enhancer additiveforming the container that increases one or more properties comprising:increasing energy conversion efficiency from photon energy to heat, orincreasing a heating rate of the material contained within, wherein theat least one photon energy absorption enhancer additive has an opticaldensity value greater than 1 for photon energy between 0.49 eV-2.38 eV(2500 nm-520 nm) after thermoplastic injection molding.
 2. A dentalmaterial heating and dispensing device for heating a dental material andapplying the heated dental material to a tooth surface or cavitycomprising: a. a device body; b. a plunger mounted movably within thedevice body for engaging with a dental material container; c. anactuation means connected to the plunger to controllably dispense thedental material from the dental material container; d. a distallymounted photon energy emission source, wherein the distally mountedphoton energy emission source consists of an electroluminescence sourcethat produces between 0.5 watts and 20 watts of optical power; e. arechargeable power source, wherein the electroluminescence source is inelectrical communication with the rechargeable power source; f. aprimary heat sink located within the device body or that constitutes apart of the device body, wherein the electroluminescence source iscoupled to the primary heat sink; and g. a receptacle on the device bodyfor securably receiving the dental material container, such that thedental material container is held within close proximity to theelectroluminescence source.
 3. The device according to claim 2, whereinthe distally mounted photon energy emission source is capable ofemitting photon energy between 0.49 eV-2.38 eV (i.e. 2500 nm-520 nm). 4.The device according to claim 2, wherein the distally mounted photonenergy emission source emits photon energy between 1.24 eV-1.77 eV (i.e.1000 nm-700 nm).
 5. The device according to claim 2, wherein theelectroluminescence source comprises a light emitting diode (LED) or alaser diode or a combination thereof.
 6. The device according to claim2, wherein the electroluminescence source is less than about 1 cm fromthe receptacle.
 7. The device according to claim 2, wherein the devicefurther comprises a collimator comprising a lens or fiber optic forincreasing a photon energy irradiance to the container having the dentalmaterial.
 8. The device according to claim 2, wherein the primary heatsink is coupled to a secondary heat sink contained within the device, orthat comprises part of a housing of the device, wherein the secondaryheat sink prevents the device from reaching an unsafe elevatedtemperature above 50° C.
 9. The device according to claim 8, wherein theprimary heat sink or secondary heat sink is coupled to a heat pipe,wherein the heat pipe prevents the device from reaching an elevatedtemperature.
 10. The device according to claim 2, further comprising aheat sensor, wherein the heat sensor prevents the device from reachingan elevated temperature, which may degrade the dental material or maypose a danger to an operator or a patient being treated with the device;wherein the heat sensor is indirectly capable of monitoring thetemperature of the dental material and reducing or removing power outputof the distally mounted photon energy emission source.
 11. The deviceaccording to claim 2, further comprising a loop control feedback systemfor maintaining a desired temperature without reaching undesirabletemperatures, which may degrade the dental material or may pose a dangerto an operator or a patient being treated with the device.
 12. Thedevice according to claim 2, further comprising an absorption sensor fordetermining the absorption characteristics of a dental material ordental material container, wherein the sensor provides an output foradjusting power and/or duration of the distally mounted photon energyemission source for achieving a desired temperature of the dentalmaterial.
 13. The device according to claim 2, further comprising anadditional light source for curing dental photopolymerizable materials.14. The device according to claim 13, wherein the additional lightsource for curing dental photopolymerizable materials emits between 500mW and 3 W of optical power.
 15. The device according to claim 13,wherein the additional light source for curing dental photopolymerizablematerials emits between 700 mW and 1.5 W of optical power.
 16. Thedevice according to claim 13, wherein a photon energy emission outputfrom the distally mounted photon energy emission source leads, lags, oris simultaneously used with a photon energy emission output of theadditional light source for curing dental photopolymerizable materials.17. The device according to claim 13, wherein the additional lightsource for curing dental photopolymerizable materials and the distallymounted photon energy emission source are arranged distally on thedevice for access to an oral cavity of a patient.
 18. The deviceaccording to claim 13, wherein the additional light source for curingdental photopolymerizable materials emits a light at a wavelength ofabout 365 nm-500 nm.
 19. A method of treating a tooth of a subject inneed thereof comprising heating a dental composite material or acontainer comprising the dental composite material with the device ofclaim
 2. 20. A handheld multispectral device for enhancing the curing ofa photopolymerizable dental material, the device comprising: a. athermally conductive body; b. at least four discrete distally mountedphoton energy emission sources that produce at least two discreteemission spectra, wherein; i. one photon energy source is centrallylocated, and at least three photon energy sources are located radiallyabout the centrally located photon energy source; ii. an output of thecentrally located photon energy emission source leads, lags, or issimultaneously used with an output of the at least three radiallylocated photon energy emission sources; iii. at least one emissionspectra is used for curing the photopolymerizable dental material, andat least one emission spectra is used to elevate the photopolymerizabledental material's temperature above ambient temperature during curing;iv. the at least four photon energy emission sources consists of lightemitting diodes; c. the at least four discrete photon energy emissionsources are coupled to at least one primary heat sink located within thedevice body; d. the at least one primary heat sink is coupled to thethermally conductive body; and e. the light emitting diodes are inelectrical communication to a direct current power source.